Substituted tetraalkyl phosphonium aluminosilicates

ABSTRACT

Novel layer type clay-like tetraalkyl phosphonium aluminosilicates can be produced by the ion exchange reaction of metal aluminosilicates with phosphonium salts. For example, layered type tetraalkyl phosphonium derivatives of clays are prepared by the reaction of sodium clays with tetraalkyl phosphonium chlorides. Substituted tetraalkyl phosphonium clays such as phosphino-, amino-, cyano- and hydroxy-alkyl derivatives are similarly synthesized. The novel compositions have unexpected microstructure, thermal stability, and thixotropic properties in organic liquids.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of U.S. PatentApplication of Ser. No. 644,810 filed Dec. 29, 1975, now U.S. Pat. No.4,053,493 which in turn is a continuation-in-part of U.S. PatentApplication of Ser. No. 402,465 which was filed on Oct. 1, 1973 andissued as U.S. Pat. No. 3,929,849 on Dec. 30, 1975.

FIELD OF THE INVENTION

This invention is related to novel quaternary onium aluminosilicates,namely layered type tetraalkyl phosphonium aluminosilicates, theirpreparation, structure and properties. More particularly, this inventionrelates to tetraalkyl phosphonium derivatives of clays of layeredstructure having a high ion exchange capacity. Specifically, thisapplication relates to phosphinoalkyl, aminoalkyl, cyanoalkyl andhydroxyalkyl phosphonium clays.

These phosphonium clays in general are related to tetraalkyl ammoniummontmorillonite clays known in the trade as organic Bentones, but theyhave unexpected interlayer structures, are thermally more stable and,dependent on their structure, show superior thixotropic properties inorganic liquids of varying polar character.

PRIOR ART VERSUS THE PRESENT INVENTION

The affinity between certain organic compounds and clays has been knownfor many years. J. U. Lloyd reported the adsorptive capacity of Fuller'searth for alkaloids in 1916 in the Journal of the AmericanPharmaceutical Association, Volume 5, pages 381 to 390 and 490 to 495.C. R. Smith reacted organic bases and their salts with bentonite andpresented evidence that the reaction involved ion exchange. (Forreference see the Journal of the American Chemical Society, Volume 56,pages 1561-1563, from the year 1934).

Quaternary phosphonium derivatives of water dispersible clays werementioned in the patent literature under the term "onium clays". Oniumclays were claimed for various uses in U.S. Pat. Nos. 2,531,396;2,531,427; 2,531,440; 2,531,812; 2,662,987; 3,671,190. The word "onium"is a cumulative term for ammonium phosphonium, arsonium, stibonium,oxonium, sulfonium and selenonium. However, the above patents coveringonium clays were specifically directed towards ammonium clays. Amongtens of thousands of the possible phosphonium clays, only the triphenyldodecyl phosphonium derivative was mentioned. The only reference to alayered quaternary tetraalkyl phosphonium clay is to dimethyldioctadecyl phosphonium bentonite in U.S. Pat. No. 2,895,954. However,this reference was apparently made by accident without any knowledge ofthe subject matter as indicated by disclosures of the nonexistentdimethyl dioctadecyl oxonium and sulfonium bentonites in the samepatent. The existence of the latter compounds would clearly violate thegenerally valid chemical valence rules, since oxonium and sulfonium ionshave only three covalent bonds. It is clear from the disclosure that theinventor used purchased dimethyl dioctadecyl ammonium bentonite to gelbituminous compositions. With regard to other "dimethyl dioctadecylonium compounds" he had an apparently incorrect assumption. Anotherreference in U.S. Pat. No. 3,709,979 is to tetrabutyl phosphoniumzeolite, i.e., an aluminosilicate having a hole and tunnel typestructure.

Although the prior art descriptions of onium clays had no structurallimitations, they were generally limited to compositions which gelhydrocarbons or are used as intermediates. For gelling, it was generallyassumed that the onium moiety should contain at least ten carbon atomsin a straight chain. See U.S. Pat. No. 2,531,426 by E. A. Hauser.Furthermore, it was claimed that the clay should have an ion exchangecapacity of at least 25 miliequivalent onium ion per 100 g.

In contrast, to the all inclusive disclosures of the patent literaturevery few onium clays were found useful in practice. All the commercialonium clays are quaternary ammonium derivatives. For many years,dimethyl dioctadecyl ammonium bentonite was the only commercial compoundin the field. For references, see J. W. Jordan and F. J. Williams,Organophylic Bentonites III, Kolloid Zeitschrift, Volume 137, pages 40to 48, 1954; J. V. Kennedy and W. T. Granquist, "Flow Properties ofDispersions of an Organo Montmorillonite in Organic Media", Nat. Lub.Grease Inst. Spokesman, Volume 29, No. 5, pages 138-145, 1965. Morerecently, dimethyl octadecyl benzyl ammonium bentonite was introduced.These two clays were useful in gelling a large variety of liquidhydrocarbons. However, they were ineffective in highly polarnonhydrocarbons such as polyesters.

The present invention is the result of a long range study of tetraalkylphosphonium clays which, at first glance, appear analogous to the knowntetraalkyl ammonium clays. Our study showed that the novel tetraalkylphosphonium clays have several unobvious, inherent properties. They arethermally more stable than their nitrogen analogs. They do not requirethe addition of polar dispersants for gelling organic liquids. They gelnonhydrocarbons just as well as hydrocarbons. Their gelling action doesnot depend on the presence of at least one straight alkyl chain having aminimum of ten carbon atoms. They have a more selective interaction withliquids which is useful in various separations.

In an apparent contrast to the known quaternary tetraalkyl ammoniumclays, the novel quaternary tetraalkyl phosphonium clays possess avariety of properties strongly dependent on the structure of thealiphatic substituents. In the area of ammonium clays, only the longchain alkyl and methyl substituted derivatives were synthesized. Most ofthese exhibited the same kind of properties. In contrast, it was foundin the present invention that, dependent on the number of long chainalkyl substituents on the phosphorus, phosphonium clays show verydifferent properties. For example, the different interplanar distance ofsuch layered clays indicates very different structures. Furthermore, itwas found that if one is to substitute ethyl, propyl and butyl groupsinstead of methyl, as the low trialkyl substituents of long chainmonoalkyl phosphonium clays, again different microstructures andproperties result.

The present invention of novel tetraalkyl phosphonium clays, of course,would not have been possible without the advance which was made in thefield of phosphonium salt clay reactants since the original patentapplication on ammonium clays was filed in 1946, (U.S. Pat. No.2,531,427). At that time, only a handful of tetraalkyl phosphonium saltswere known. Only triphenyl alkyl phosphonium salts were available. Noneof them were attractive for the preparation of organo-clay gellants. Inthe meantime, many tetraalkyl phosphonium salts became known.Nevertheless, most of the surprisingly attractive phosphonium claygellants of the present invention are based on novel tetraalkylphosphonium salts. The latter were synthesized during the course ofconcurrent work in alkyl phosphine and phosphonium salt chemistry in thebroadest context of the same long range research program which led tothis invention. These novel, intermediates are (will be) covered by U.S.Pat. No. 3,998,754 and related patent applications.

In summarizing the prior art, it is pointed out that onium clays weredisclosed in several patents which include all phosphonium clays ever tobe made. However, there was nothing specific known about tetraalkylphosphonium clays. In view of this and the surprising differencesbetween tetraalkyl phosphonium clays of the present application and theknown tetraalkyl ammonium clays of the prior art, the presentcompositions are patentably distinct from those of the prior art.

Investigations were carried out with the novel tetraalkyl phosphoniumclay compositions with regard to their usefulness as thixotropic agentsin various areas, as separation and complexing agents, and asreinforcing agents.

SUMMARY OF THE INVENTION

Onium clays in general, possess properties which make them compatiblewith organic compounds. Certain tetraalkyl ammonium clays, inparticular, are effective as hydrocarbon gelling agents. The usefulnessof such ammonium clays stimulated this work with the aim of discoveringnovel onium clays.

In the present invention, new types of tetraalkyl phosphonium clays aredisclosed. Their preparation from the corresponding phosphonium saltsand inorganic clays in also described. These clays have unexpectedstructures as determined by X-ray. Furthermore, they have unexpectedproperties such as thermal stability and selective interaction withorganic liquids and vapors. Due to these properties, they were foundsurprisingly useful as thixotropic, reinforcement and separation agents.

PRODUCT COMPOSITIONS

The tetraalkyl phosphonium clay compositions of the present inventionhave four C₁ -C₁₀₀ aliphatic hydrocarbyl or substituted aliphatichydrocarbyl moieties attached to their phosphorus atom. The positivecharge of the phosphonium cations of such compositions is balanced bynegatively charged clay particles of various charge densities. Theseclays are modified natural or synthetic metal aluminosilicates.

As such tetraalkyl phosphonium clays can be defined by the formula [R₄P⁺ ]_(e) Clay^(-e) wherein e is the number of the negative charges onthe clay particle which are neutralized by phosphonium cations. Such anumber is dependent on the clay particle size and as such cannotunequivocally be determined. Consequently, the simplified formula of thephosphonium clays is [R₄ P⁺ ] Clay⁻, wherein R is C₁ -C₁₀₀ aliphatichydrocarbyl or substituted aliphatic hydrocarbyl, preferably C₁ -C₄₀alkyl or monosubstituted alkyl. In a preferred type of phosphonium clay,at least one of the R groups is substituted aliphatic hydrocarbyl.

The term "aliphatic hydrocarbyl" includes saturated, open chain andcyclic alkyl groups. It also includes similar unsaturated, i.e., alkenyland alkinyl groups. The substituents of the aliphatic hydrocarbonsinclude all those moieties which are compatible. Such substituents canbe aromatic groups such as phenyl and heteroaromatic groups, such asphenyl and their derivatives. They can be halogens, i.e., F, Cl, Br, I.They can represent heteroatomic radicals such as oxygen, orsulfur-containing groups, e.g. hydroxy, carbonyl, carboalkoxy, thiol,thioether, sulfone, sulfonate. They can contain nitrogen heteroatom,e.g. in the form of amino, cyano, nitrite, nitrate, amido groups. Theycan also contain organic silicon heteroatom, preferably as a silane.Phosphorus-heteroatom containing groups, such as phosphine oxide,phosphate, phosphite, phosphonate, phosphinate, are also included.Dependent on their character, such heteroatomic substituents may beeither inserted into the aliphatic chain as ethers or can take the placeof one or more hydrogens on the aliphatic carbon chain or on an aromaticmoiety, as halogens do. Although the various aliphatic hydrocarbylgroups can be substituted, for many uses the unsubstituted groups arepreferred. The preferred substituents however, are selected from thegroup consisting of phosphino-, amino-, cyano-, and hydroxy groups.

Quaternary phosphonium groups may be covalently bound by di- orpolyvalent aliphatic radicals to form diphosphonium and polyphosphoniumcompounds. These in turn can be also converted to phosphonium clays.

Examples of the aliphatic hydrocarbyl groups include methyl, ethyl,i-propyl, t-butyl, n-dodecyl, docosyl, squalyl, triacontyl,hexatriacontyl, C₁₀₀ alkyl derived from isobutylene oligomer;cyclopentyl, cyclododecyl; vinyl, allyl, propargyl, cyclohexenyl,methylcyclopentenyl, benzyl, chlorobenzyl, phenylethyl, dodecylbenzyl,tetrahydronaphthyl, phenoxybenzyl, benzothiazylthiomethyl; chloroethyl,iodobenzyl; dichloroallyl, perfluoroundecyl, bromotetradecyl,hydroxymethyl, hydroxyethyl, hydroxypropyl, epoxypropyl,carbomethoxyethyl, hydroquinonethiomethyl, acetylbenzyl, mercaptopropyl,hexacosylthiopropyl, aminopropyl, diethylaminopropyl,triacontylaminoethyl, N-morpholinoethyl, cyanoethyl, nitrobenzyl,diphenylphosphinodecyl.

One of the preferred class of compositions has at least one, preferablythree saturated, unsubstituted alkyl groups. In this class of compounds,it is furthermore preferred that the fourth aliphatic group be alkyl,alkenyl, alkinyl or monosubstituted derivative thereof.

Furthermore, it is preferred that at least one of the aliphatichydrocarbyl groups should contain at least 8 carbon atoms. This higheraliphatic group is preferably a saturated alkyl group.

The aliphatic substituents of the phosphonium groups can beindependently selected. Some of the more common selections are indicatedby the tabulation on pages 217 to 467 in the monograph on OrganicPhosphorus Compounds, edited by G. M. Kosolapoff and L. Maier, Volume 2,Chapter 4 by P. Beck, published by J. Wiley & Sons, Inc. 1972, in NewYork. The most common types of these selections are indicated by theformula:

    [R.sub.4.sup.1 P.sup.+ ]X.sup.- [R.sub.3.sup.1 P.sup.+ R.sup.2 ]X.sup.- [R.sub.2.sup.1 P.sup.+ R.sub.2.sup.2 ]Cl.sup.- [R.sub.2.sup.1 P.sup.+ R.sup.2 R.sup.3 ]X.sup.- [R.sup.1 R.sup.2 P.sup.+ R.sup.3 R.sup.4 ]X.sup.- R.sup.1 R.sup.2 P.sup.+ R.sup.5 R.sub.3.sup.1 P.sup.+ R.sup.6 P.sup.+ R.sub.3.sup.2

wherein R¹ to R⁴ have the same meaning as P; R⁵ and R⁶ are divalentaliphatic radicals, preferably alkylene, alkenylene, alkinylene andtheir substituted derivatives in the C₁ to C₄₀ preferably C₁ to C₁₄range.

Examples for divalent radicals are ethylene, butenylene, butinylene,cyclohexylene, octamethylene, tetradecamethylene, triacontylene,hydroxymethylethylene, o-chloroxylylene.

The preferred quaternary phosphonium groups in the simple salt form,e.g. as chlorides, are surface active. There is a correlation betweenthe surfactant activity of the salts and the gellant activity of theclay derivatives. Consequently, detergent range n-alkyl groups arepreferred phosphorus substituents for phosphonium clays.

Tetraalkyl phosphonium clays can be further classified according to thenumber of high and low alkyl substituents of the phosphonium group. Ingeneral, low alkyl groups mean aliphatic substituents having up to 7carbon atoms. High alkyl groups possess a minimum of 8 carbons.

A preferred class of phosphonium clay compositions is of the followingformula: [R'₃ P⁺ R"] Clay⁻, wherein R' and R" are aliphatic hydrocarbylradicals selected from the group consisting of C₁ -C₇ low aliphaticradicals and C₈ -C₁₀₀ high aliphatic radicals and their substitutedderivatives in such a manner that if R' is low aliphatic, R" should behigh aliphatic and the reverse. The high aliphatic radicals arepreferably C₈ -C₄₀ alkyl groups. The low unsaturated radicals arepreferably selected from C₁ -C₇ aliphatic radicals consisting of alkyl,alkenyl, alkinyl and monosubstituted derivatives thereof, particularlymonosubstituted alkyl.

Another class of phosphonium clay compositions is represented by theformula: [R₂ 'P⁺ R₂ "] Clay⁻, wherein the meaning of R' and R" is thesame. Some of the preferred compositions of this type are wherein the R'groups are C₉ -C₂₀ alkyl groups, one R" group is a C₁ -C₄ alkyl and theother R" is C₁ -C₄ alkyl, C₁ -C₄ monosubstituted alkyl, C₂ -C₄ alkenyl,C₂ -C₄ alkinyl. Even more specifically preferred compositions are thosehaving R' as C₉ -C₁₆ alkyl and R" as C₁ -C₂ alkyl.

Among the unsubstituted tetraalkyl phosphonium clays there are alsopreferred high mono-, di- and trialkyl derivatives.

Preferred types of high monoalkyl phosphonium clays are of the formula:

    [C.sub.m H.sub.2m+1 P.sup.+ (C.sub.n H.sub.2n+1).sub.3 ] Clay.sup.-

wherein m is 12 to 40, more preferably, 16 to 30, most preferably 20 to30 and n is 1 to 4, preferably 3 to 4.

Preferred types of higher dialkyl phosphonium clays are of the formula:

    [(C.sub.r H.sub.2r+1).sub.2 P.sup.+ (C.sub.s H.sub.2s+1).sub.2 ] Clay.sup.-

wherein r is 8 to 40, preferably 14 to 20, most preferably 18, s is 1 to7, preferably 1 to 4. Preferably at least one of the two low alkylgroups is other than methyl.

Preferred types of higher trialkyl phosphonium clays are of the formula:

    [C.sub.k H.sub.2k+1 P.sup.+ (C.sub.j H.sub.2j+1).sub.3 ] Clay.sup.-

wherein j is 6 to 40, preferably 8 to 18; most preferably 8, 9 or 16 to18, k is 1 to 4, preferably 4.

The high alkyl phosphonium clays of the present invention include aspreferred compositions, those of unsymmetrical structure. Specifically,preferred unsymmetrical high monoalkyl phosphonium clays are those ofthe formula: ##STR1## wherein R"' is a C₁ to C₄ aliphatic hydrocarbyl,preferably a C₁ to C₄ alkyl group different from C_(n) H_(2n+1). It ismost preferred that R"' be methyl or ethyl. Similarly, preferredunsymmetrical high dialkyl phosphonium clays are of the formula:##STR2## wherein the meaning of R"', s and r are as above.

Another preferred type of higher alkyl phosphonium clays has at leastone unsaturated low hydrocarbyl, preferably allylic substituent.Specifically, preferred classes of compounds are of the formula:##STR3##

Similar phosphonium clays having a reactive substituent may haveacrylate, hydroxy, thiol, amino, silane, halogen, cyano, styryl andother similar functional groups.

Preferred type of tetraalkyl phosphonium clays have at least onesubstituent on at least one of the alkyl chains. Such a substituent ispreferably selected from the group consisting of phosphino, amino, cyanoand hydroxy substituents. The phosphino group is preferably C₁ -C₄₀dihydrocarbyl phosphino, more preferably diaryl phosphino, mostpreferably diphenyl phosphino. The amino group is preferably --NH₂, C₁-C₄₀ alkylamino and dialkylamino, more preferably, C₂ -C₁₈ dialkylamino.The phosphino group can be free or complexed with transition metalcompounds.

The total number of carbon atoms of each alkyl group of theabove-substituted tetraalkyl phosphonium salts is C₁ -C₁₀₀ as previouslystated. It is preferred that at least one of these alkyl groups containat least 8 carbon atoms. This higher aliphatic group is preferably asaturated, nonsubstituted alkyl group.

The divalent aliphatic group bridging the phosphonium phosphorus and thesubstituting group can possess from one to forty carbons. It can beeither a low aliphatic group of the C₁ -C₇ range or a higher aliphaticgroup, preferably in the C₈ -C₄₀ range. In most cases, it is preferredthat the substituting group be on the low aliphatic group. A preferredclass of low aliphatic groups includes C₁ -C₆ divalent alkylene andalkenylene groups. The higher aliphatic groups are preferably of thepolymethylene type.

Besides the higher alkyl and the substituted alkyl groups, this type ofphosphonium clays may preferably contain an unsaturated low alkyl group,most preferably, an allylic group.

Accordingly, the general formulae of this preferred type of substitutedtetraalkyl phosphonium clays are:

    {R.sub.x P.sup.+ [QZ].sub.y }Clay.sup.-

wherein R is a C₁ -C₁₀₀ monovalent aliphatic hydrocarbyl radical,preferably C₁ -C₁₀₀ aliphatic hydrocarbyl radical selected from thegroup consisting of alkyl and alkenyl, more preferably, a C₁ -C₁₀₀alkyl, most preferably at least one R is a C₂ -C₁₀ aliphatichydrocarbyl; Q is a C₁ -C₁₀₀ divalent aliphatic hydrocarbyl radical,preferably a C₁ -C₄₀ divalent aliphatic radical selected from the groupconsisting of alkylene and alkenylene; Z is a heteroatomic radicalcontaining up to 40 carbon atoms preferably selected from the groupconsisting of phosphino, amino, cyano and hydroxy groups, morepreferably selected from the group consisting of diphenyl phosphino,--NH₂, C₄ -C₁₈ dialkylamino, wherein x and y are 1 to 3, preferably 1 or3, providing that x plus y equals 4.

If there are several R groups, they are independently selected. It ispreferred that at least one of the R groups be a C₈ -C₁₀₀ high aliphatichydrocarbyl radical, preferably alkyl radical and be unsubstituted. Therest of the R groups are preferably C₁ -C₇ low aliphatic hydrocarbylradicals, more preferably selected from the group of alkyl and alkenylradicals, most preferably alkyl radicals. There is a specific preferencefor compounds wherein the low aliphatic hydrocarbyl radicals are alkylexcept one which is a C₃ -C₅ allylic radical, most preferably allyl.

A preferred subgeneric composition comprises diphenylphosphinosubstituted tetraalkyl phosphonium clays of the formula: ##STR4##wherein z is 1 to 40, preferably 6 to 14 and the other symbols are aspreviously defined.

Another preferred subgeneric composition comprises amino substitutedtetraalkyl phosphonium clays of the formula:

    {R.sub.x P.sup.+ [(CH.sub.2).sub.z N(C.sub.q H.sub.2q+1).sub.2 ].sub.y }Clay.sup.-

wherein q is 0 to 18, preferably 1-18, more preferably 2-18, mostpreferably 2-4; and the other symbols are as previously defined exceptthat the most preferred value of z is 3.

A third preferred subgeneric composition comprises cyano-substitutedtetraalkyl phosphonium clays of the formula:

    {R.sub.x P.sup.+ [(CH.sub.2).sub.z CN].sub.y }Clay.sup.-

wherein the symbols are as previously defined, the most preferred valueof z being 2.

A fourth preferred subgeneric composition comprises hydroxy substitutedtetraalkyl phosphonium clays of the formula:

    {R.sub.x P [(CH.sub.2).sub.z OH].sub.y }Clay.sup.-

wherein the symbols are as previously defined, the specificallypreferred range of z being 1 to 3.

Examples of the unsubstituted aliphatic phosphonium groups on claysinclude docosyl trimethyl phosphonium, hexatriacontyl tricyclohexylphosphonium, octadecyl triethyl phosphonium, docosyl triisobutylphosphonium, methyl trinonyl phosphonium, ethyl trihexadecylphosphonium, dimethyl didecyl phosphonium, diethyl dioctadecylphosphonium, octadecyl diethyl allyl phosphonium, trioctyl vinylbenzylphosphonium, octyl nonyl decyl propargyl phosphonium, bis-trioctylethylene diphosphonium, bis-(diethyloctadecyl) xylylene diphosphonium,etc.

Examples of the phosphine substituted aliphatic phosphonium groups onclays include diphenylphosphinodecyl dihexadecyl methyl phosphonium,ditolylphosphinoethyl benzyl trioctyl phosphonium,dibiphenylylphosphinohexyl docosyl i-butyl methyl phosphonium,tris-diphenylphosphinopropyl benzyl phosphonium,bis-cyclohexylphosphinotetradecyl trimethyl phosphonium,bis-t-butylphosphinoethylphenyl ethyl trimethyl phosphonium.

Examples of the amine substituted aliphatic phosphonium groups on claysare the following: tris-aminopropyl docosyl phosphonium,bis-diethylaminotetradecyl, eicosyl ethyl phosphonium,diisopropylaminopropyl diisobutyl benzyl phosphonium,phenylethylaminoundecyl dicyclohexyl methyl phosphonium,tris-benzylaminopropyl dodecyl phosphonium, trioctyl dimethylaminopropylphosphonium.

Examples of the cyano-substituted aliphatic phosphonium groups onaluminosilicates are the following: triscyanoethyl hexadecylphosphonium, bis-cyanopropyl dodecyl allyl phosphonium, cyanododecyltrinonyl phosphonium, bis-(triscyanoethyl) ethylene diphosphonium,cyanoethyl dodecyl dicyclohexyl phosphonium, triacontyl tris-cyanoethylphosphonium.

Examples of the hydroxy substituted phosphonium groups of clays are:tris-hydroxymethyl tetracosyl phosphonium, tris-hydroxyethyldodecylbenzyl phosphonium, tris-hydroxypropyl octadecyl phosphonium,hydroxypropyl trioctyl phosphonium, hydroxyethyl dicyclohexyl crotylphosphonium, hydroxydecyl triethyl phosphonium, eicosyltrihydroxymethylphosphonium.

Examples of miscellaneous substituted phosphonium groups claysubstituents are: triisobutyl perfluoroundecyl phosphonium,tris-acetoxyethyl docosyl phosphonium, tris-carbamidoethyl dodecylphosphonium, tris-carboxyethyl hexadecyl phosphonium,tris-carboethoxyethyl eicosyl phosphonium, dichlorobenzyl diethyldocosyl phosphonium, dibromobenzyl trioctyl phosphonium,tris-chloroallyl eicosyl phosphonium, tris-thiopropyl dodecylbenzylphosphonium, trimethylsilyldodecyl diisobutyl decyl phosphonium,tris-dibromoallyl benzyl phosphonium.

The modified Clay⁻ groups of the present phosphonium compositions arebest defined in terms of the layer type natural and synthetic metal andammonium aluminosilicates from which they are derived.

The natural clay starting materials of the present invention are finegrained metal aluminosilicates which develop plasticity when mixed withlimited amounts of water. For a more detailed definition andclassification of clays, see the monograph entitled Clay Mineralogy byR. E. Grim, published by McGraw-Hill, Inc., New York, in 1968,particularly Chapters 1 to 3 on pages 1 to 50. Similar synthetic clayderivatives are also included. Preferred synthetic clay-like mineralsare described in U.S. Pat. No. 3,671,190.

In general, sodium aluminosilicate clays are preferred for thederivation of the present phosphonium clays. The preferred clays havehigh cation exchange capacities and are crystalline. Among the preferredclays are those having crystalline layer type structures. For example,the three-layer type sodium montmorillonite clays can be advantageouslyused. Synthetic montmorillonites, e.g. laponites, are also suitable.Another useful clay is the chain structure type attapulgite. Two layertype clays such as kaolinites can be also used. Zeolites, i.e., metal orammonium aluminosilicates having a tunnel-hole structure, are notincluded in the term "clay" as it is used in the present invention.

Further examples of clays are halloysite, smectite, illite, vermiculite,chlorite, sepiolite, palygorskite, saponite, montronite, muscovite,beidellite, biotite, micas, talcum, batavite, allevardite, stevensite,amesite.

PROCESS OF PRODUCT PREPARATION

The above described clays, i.e., metal aluminosilicates, particularlythe more reactive ammonium and sodium aluminosilicate clays, are used asstarting materials in the present process. These clays are reacted withtetraalkyl phosphonium salts to form the corresponding quaternaryphosphonium salt products. The phosphonium salt reactants are of theformula: y[R₄ P⁺ ] X^(-y), wherein y is the number of the valency of theanion, i.e., 1 to 5, preferably 1 to 3; most preferably 1 X is an anion,preferably an anion derived from protic acids. Examples of X arehalogen, i.e., chlorine, bromine, fluorine, iodine, sulfate, sulfonate,phosphate, phosphonate, phosphite, carboxylate, such as acetate.

The clay starting materials are usually reacted in the form of asuspension. The preferred suspending agent is water. Aqueous alcoholscan be also used. The lower alcohols, having 1 to 3 carbon atoms, can bealso used. It may be advantageous at times to use a hydrocarbon such asheptane, together with the aqueous medium, since the phosphonium clayproducts are usually more compatible with hydrocarbons than water.

The phosphonium salt reactants can be added to the clay suspension assuch or as a solution. Suitable exemplary solvents are water, alcohols,ketones, hydrocarbons. A water miscible solvent is usually preferred. Onthe addition of the phosphonium salt to the clay, ion exchange takesplace. If the X⁻ anion of the salt and the Me cations of the clay aremonovalent, the reaction can be simply described by the followingscheme:

    [Clay.sup.-e ] eMe.sup.+  + e {[R.sub.4 P.sup.+ ]X.sup.- } → [R.sub.4 P.sup.+ ].sub.e Clay.sup.-e

wherein Me is metal, ammonium, hydrogen, preferably metal.

This reaction can be carried to full or partial conversion. The term"full conversion" means that all the exchangeable metal cations areexchanged for phosphonium cations. The amount of exchangeable metals isusually given in miliequivalents per 100 g clay and is designated as ionexchange capacity. The amount of phosphonium salt may exceed the ionexchange capacity of the clay. In such cases, the "excess" phosphoniumsalt is complexed with the phosphonium clay.

An advantageous method for the preparation of the tetraalkyl phosphoniumclays consists of adding the corresponding phosphonium salt to anaqueous suspension of the clay. The phosphonium salt is preferably addedas a solution in water or in alcohol. As a result of the ion exchange,the clay usually becomes less hydrophylic and precipitates from thewater. The metal salt by-product of the exchange is usually watersoluble. Consequently, the tetraalkyl phosphonium clay products can beusually separated as crystalline solids by simple filtration andwashing.

The ion exchange reaction is rather independent of the reactiontemperature. The temperature is preferably above the crystallizationpoint of the medium and below its boiling point. For aqueous systems thetemperature is between 0 and 100° C., preferably between 40° and 80° C.

The occurrence of the reaction is also rather independent of theconcentration of the reactants. The ion exchange goes to completion evenin extremely dilute media. Nevertheless, if the reaction is carried outfor manufacturing purposes, practicality commands a lower limit ofreactant concentration at about 0.1%. The higher limit is usually set bythe viscosity a of the thixotropic clay suspension, usually at 7.0%. Thepreferred clay concentrations are in the range of 0.5 and 10%. It ismost often preferred to operate in the 1 to 5% clay concentration range.The concentration of the phosphonium salt when added is immaterial. Theonly significance of the solvent here is in aiding the mixing with theclay suspension and adjusting the final solvent concentration in thereaction mixture.

PRODUCT PROPERTIES

The tetraalkyl phosphonium clays of the present invention have manyunexpected properties. Some of these properties are common to all theproducts and distinguish them from analogous tetraalkyl ammonium clays.Other unexpected properties are dependent on the presence of particularaliphatic substituents. A general discussion of these properties will beprovided in the following.

The thermal stability of all the tetraalkyl phosphonium clays is greaterthan that of their ammonium analogs. The difference in thermal stabilitybecame apparent when the quaternary clay samples were heated up to 900°C. at a certain rate under nitrogen. Under these conditions, thetemperature and the rate of the weight loss of the sample reflect itsthermal stability. Such studies showed that the phosphonium clays on anaverage suffered comparable weight loss at temperatures about 80° C.higher than those observed for the ammonium analogs at the same heatingrate. Furthermore, it was found that tetraalkyl phosphonium clays havinghigher than methyl substituents were thermally more stable under theseconditions than similar derivatives having methyl substituents.

The affinity of tetraalkyl phosphonium clays towards polar compounds ishigher than that of their nitrogen analogs. This property may beconnected with more facile, and more stable complex formation in thecase of the phosphonium clays. Due to this, tetraalkyl phosphonium claysare more active gelling agents for polar organic compounds such asaromatic hydrocarbons, and oxygenated compounds. Also, tetraalkylphosphonium clays do not require polar additives as the ammonium analogsdo when used as gelling agents.

The above affinity is responsible for the comparatively long retentionof aromatics when passed through gasliquid chromatography (glc) columnspacked with phosphonium clays. Furthermore, probably for the samereason, silicon modifiers are not necessary when phosphonium rather thanammonium clays are used in such glc separations.

There are also unexpected differences between the microstructure of thevarious types of quaternary tetraalkyl phosphonium clays. Thismicrostructure refers to the orientation of the quaternary phosphoniumgroups between the inorganic aluminosilicate layers. The repeat distanceof these layers in the original clays and in their various quaternaryderivatives could be determined by X-ray. Comparing these distances, thechanges of the interlayer distances could be determined. It was foundthat the increase of these distances could be directly related to thecarbon number of the higher n-alkyl substituents on the phosphorus.Furthermore, it was surprisingly found that these distances also dependon the number of higher n-alkyl groups per phosphorus atoms. Obviouslythe orientation of the phosphonium groups and particularly theorientation of the higher n-alkyl substituents depends on the number ofhigher n-alkyl groups per phosphorus.

The above dry microstructure of the quaternary higher monoalkylphosphonium clays is such that the interplanar spacing is moderatelyinfluenced by the number of carbons of the n-alkyl groups. Such amoderate effect can be visualized by the orientation of alkyl groups ata small angle to the aluminosilicate plane. In the case of quaternaryhigher dialkyl phosphonium clays, this effect on the spacing of thenumber of carbons per n-alkyl group is more pronounced. Accordingly, alarger angle between the n-alkyl groups and the layer plane is assumed.In the case of the quaternary higher trialkyl phosphonium clays, thiseffect is even higher and can be explained by a perpendicularorientation of the higher n-alkyl groups.

As a consequence of the above microstructures, the required number ofcarbon atoms per higher n-alkyl substituent for gelling is much smallerfor higher trialkyl than higher monoalkyl phosphonium clays.Furthermore, due to this structure, C₁₋₃ alkyl C₇₋₉ trialkyl phosphoniummontmorillonites are especially capable of interacting with highly polargroups such ester groups. On the other hand, quaternary phosphoniumcompounds having only one C₁₂ or higher alkyl groups per phosphoniummoiety are particularly apt to interact with hydrocarbons such astoluene.

Thus, the gelling properties of the layered high alkyl phosphonium claysof high ion exchange capacity, particularly of the montmorillonite typeclays, highly depend on the number and carbon range of higher alkylgroups. Also, different types of phosphonium clays exhibit optimumgellant interactions in organic fluids of different polarity.

High monoalkyl phosphonium clays possess superior gellant properties inhighly polar media, particularly when overtreated. Their optimum gellantinteraction is in the C₂₀ -C₂₂ carbon range of higher alkyl groups.Choice polar fluids are alkyd type polyesters, lubricant diesters,polyesters and polyphenyl ethers.

High dialkyl phosphonium clays are particularly outstanding gellants inmedia of relatively medium polarity such as aromatic hydrocarbons andunsaturated polyesters. Their optimum gellant properties are in the C₁₆-C₁₈ carbon range.

High trialkyl phosphonium clays show excellent gellant properties inboth highly polar and nonpolar media if the number of carbon atoms perhigh alkyl groups is in the right range. Tri-C₈ and -C₉ derivativesexhibit excellent gellant interaction with alkyd resins while tri-C₁₄ toC₁₈ derivatives will gel paraffinic poly-α-olefin lubricants such aspolydecene.

The unexpected gelling properties of the present tetraalkyl phosphoniumclays in organic liquids can be utilized by using individual phosphoniumclay compositions or mixtures thereof. Mixtures of phosphonium clayswith other gelling agents such as ammonium clays and silica can be alsoused. Such mixtures are particularly advantageous for gelling complexsystems such as paints.

Unexpectedly, tetraalkyl phosphonium clays substituted with polar groupssuch as hydroxy exhibit excellent gellant properties. While maintainingthe gellant properties, which are often important, e.g. in the coatingsapplication of organoclays, such substituted tetraalkyl phosphoniumclays may interact with the substrate to be gelled. For example, thehydroxy substituent of phosphonium clays can react with the epoxidegroups of epoxy resin systems.

Additionally, substituted tetraalkyl phosphonium clays often possessunique complexing properties. For example, tertiary phosphino andaminoalkyl phosphonium clays complex transition metal compounds,particularly compounds of Group VIII metals, via coordinative bondingbetween their trivalent phosphorus or nitrogen and the transition metal.Such complexes represent a unique group of transition metal complexcatalysts, wherein the phosphine or amine ligand is anchored to thealuminosilicate via the ionically bound quaternary phosphonium group.Such layered clay catalysts having at least one high alkyl substituentare preferred because their ability to gel increases their effectivesurface.

EXAMPLES

General Procedures for the Preparation of Tetraalkyl

Phosphonium Montmorillonite Clays (Examples 1, 3-11)

The procedures for the preparation of phosphonium montmorillonite claystake advantage of the ready dispersability of such hydrophylic clays inwater and in water isopropanol mixtures. The composition of the mediumis dependent on the solubility of the tetraalkyl phosphonium chloridesalt clay reactant to be used. Usually it was attempted to prepare a 10%solution. If the salt was water soluble, water was used to disperse theclay reactant as well. If warm water did not dissolve the salt,isopropanol was added. Isopropanol-water mixtures were used, up to 50%isopropanol concentration as solvents for salts. Once a solution wasmade, a solvent medium of matching composition was made for dispersingthe clay.

The salt solutions were added to the stirred clay suspensions of 1 to 3%concentration which were prewarmed to 50° C. The temperature of the saltsolution was ambient in cases of high solubilities. Salts of lowersolubility were reacted as 45°-50° C. solutions as required. All thesolution was added at once. This resulted in an instantaneous reaction.Nevertheless, stirring of the reaction mixture was continued to completethe reaction and to obtain a homogeneous solid product. The product wasusually hydrophobic, large in particle size and ready to filter.Nevertheless, it retained a large (about ninefold) amount of water whichwas removed by drying in vacuo.

The phosphonium chloride reactants were usually employed in amountscorresponding to the ion exchange capacity of the clays. As a rule,complete ion exchange occurred and product analyses showed that theorganic content of the clays was close to the calculated value. Thechlorine contents were minimal, indicating that after reaction withsodium montmorillonite, the chloride anion of the phosphonium salt wasremoved as an aqueous sodium chloride filtrate.

One of the most characteristic properties of individual phosphoniumclays is their X-ray spectrum. From the X-ray data, the repeat distancesof the layered phosphonium clays can be calculated. These distances arerecorded and discussed since they depend on the structure of thephosphonium moieties which are between the inorganic aluminosilicatelayers.

EXAMPLE 1 -- Preparation of Tetraalkyl Phosphonium Hectorites

The starting clay was a refined sodium hectorite supplied by N. L.Industries. Its composition can be expressed by the following summaryformula:

    (HO).sub.4 Si.sub.8 Mg.sub.5.34 Li.sub.0.66 Na.sub.0.66

This clay was indicated to have an exchangeable ion capacity of 100milliequivalents per 100 g dry material. Accordingly, 0.1 mole ofphosphonium chloride per 100 g clay was used to effect the exchange ofthe inorganic cations of the clay for the organic phosphonium cations.

The products derived from the reaction of a number of higher monoalkyland trialkyl phosphonium chlorides are shown in Table I.

The higher monalkyl phosphonium chlorides could be dissolved in water toform 5% solutions which were then added dropwise to a well stirred 2%aqueous suspension of the clay at room temperature. Flocculation oflarge clay aggregates started immediately and stirring became difficultduring the first part of the addtion. By the time the addition wascomplete, the mixture was easy to stir. After an hour mixing, themixture was filtered readily by suction and washed by distilled water.

Among the first higher trialkyl phosphonium chlorides, only the firstone was water soluble. The others were dissolved in a 1 to 1 mixture ofwater and isopropanol and in these cases a similar solvent mixture wasused to suspend the hectorite starting clay. In the case of the methyltrihexadecyl phosphonium chloride, it was also necessary to use a highertemperature of 70° C. to effect solution. In that case, the reaction wasalso carried out at the elevated temperature. The tetraalkyl phosphoniumhectorite clay products were dried in vacuo at 0.1 mm at roomtemperature. The dry products were then analyzed for elementalcomposition and X-ray spectra.

As it is shown by Table I, the found composition of the modified claysis surprisingly close to the values calculated assuming the exchange of100 miliequivalent metal for phosphonium per 100 g of clay. Also, inthose cases wherein a 50% excess of the quaternary phosphonium saltreactant was used, the found composition rather well agreed with

                                      TABLE I                                     __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION (.sup.d 001) AND COMPOSITION OF         CLAYS MODIFIED WITH VARIOUS HIGHER MONO- AND TRIALKYL                         PHOSPHONIUM CHLORIDES                                                         Structure of Quaternary                                                                         Spacing                                                                            Elemental Composition of Modified Clay                 Seq.  Chloride Clay Modifier                                                                    .sup.d 001                                                                         Calc'd. for 100.sup.(b) (150.sup.d)me                                                      Found                                     Type                                                                             No.                                                                                100 me.sup.(a)                                                                          A    C  H  P  Cl.sup.(d)                                                                        C  H  P  Cl                               __________________________________________________________________________    I  1  (No Modifier, Starting                                                                    12.6                      0.25                                    clay)                                                                                                      13.42                                                                            2.94                                                                             2.22                                                                             0.05                              II 3  [(CH.sub.3).sub.3 P.sup.+ C.sub.12 H.sub.25 ]Cl.sup.-                                     16.1 14.74                                                                            2.80                                                                             2.53                                                                             -- 14.13                                                                            2.74                                                                             2.75                                                                             0.41                                 4  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.12 H.sub.25 ]Cl.sup.-                              17.6 17.10                                                                            3.19                                                                             2.45                                                                             -- 16.63                                                                            3.23                                                                             2.53                                                                             0.47                                 5  [(C.sub.2 H.sub.5 ).sub.3 P.sup.+ C.sub.18 H.sub.37 ]Cl.sup.-                             22.4 21.37                                                                            3.14                                                                             2.30                                                                             -- 22.10                                                                            4.05                                                                             2.41                                                                             0.79                                 6  same as above but 150                                                         me.sup.(c)  23.0 27.86                                                                            4.09                                                                             2.99                                                                             1.14                                                                             28.25                                                                            4.86                                                                             3.27                                                                             1.30                                 7  [(C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.18 H.sub.37 ]Cl.sup.-                              23.0 26.48                                                                            4.74                                                                             2.28  26.09                                                                            4.72                                                                             2.46                                                                             0.63                              III                                                                              10 [(C.sub.8 H.sub.17).sub.3 P.sup.+ CH.sub.3 ]Cl.sup.-                                      23.2 22.05                                                                            3.96                                                                             2.27                                                                             -- 24.83                                                                            4.34                                                                             2.76                                                                             0.45                                 11 [(C.sub.16 H.sub.33).sub.3 P.sup.+ CH.sub.3 ]Cl.sup.-                                     30.5-31.5                                                                          34.63                                                                            6.04                                                                             1.82                                                                             -- 32.64                                                                            5.62                                                                             2.05                                                                             0.67                                 12 same as above, but 150                                                        me.sup.c    32.5 42.47                                                                            7.42                                                                             2.23                                                                             0.85                                                                             38.82                                                                            7.20                                                                             2.34                                                                             1.18                                 13 [(C.sub.8 H.sub.17).sub.3 P.sup.+ C.sub.2 H.sub.5 ]Cl.sup.-                               21.0 22.68                                                                            4.10                                                                             2.25                                                                             -- 21.81                                                                            4.09                                                                             2.24                                                                             0.20                                 14 same as above, but 150                                                        me.sup.c    22.6 29.38                                                                            5.31                                                                             2.92                                                                             1.11                                                                             25.35                                                                            4.90                                                                             2.75                                                                             0.49                              __________________________________________________________________________     .sup.(a) Stoichiometric amount of quaternary was used assuming 100            miliequivalent cation exchange capacity for 100 g of clay                     .sup.(b) Composition calculated assuming complete ion exchange,               .sup.(c) Stoichiometric amount of quaternary was used assuming 150            miliequivalent cation exchange capacity for 100 g of clay.                    .sup.(d) Composition calculated assuming 100 me phosphonium exchange plus     50 me phosphonium halide absorption.                                     

the one calculated assuming a complete complexing of the excessphosphonium salt. There is no apparent difficulty of ion exchange forthe butyl higher trialkyl phosphonium salts.

Table I also shows some X-ray data, i.e., the interplanar spacings ofthe 001 reflection. These spacings indicate the interlayer repeatdistances. The products were examined by powder X-ray diffraction usinga Norelco goniometer with Cu radiation. All of the derivatives showedthe characteristic diffraction pattern of a clay that had beenintercalated. The specific features of the X-ray pattern were: generallybroadened peaks, a series of three to four hk0 line which did not shiftwith the different intercalates, and the 001 reflection. The interplanarspacing of the 001 reflection (^(d) 001) is dependent on the amount,geometry and orientation of the intercalating species. The unmodifiedclay has ^(d) 001-12.6 A while the modified clays have ^(d) 001 rangingfrom 15.5 A to 32.5 A. Some samples are more crystalline than others.This is indicated by a range of values for ^(d) 001. It should also benoted that the samples that were treated with an excess of salt gave asharper X-ray pattern than those treated with a stoichiometric amount ofsalt. This may be due to an incomplete coverage of the clay surface inthe absence of excess quaternary reactant.

In the case of both the higher monoalkyl (Type II) and higher trialkyl(Type III) phosphonium clays, the interplanar spacing increased with theincreased number of carbons per long alkyl group. However, for acomparable number of carbon atoms per chain, the higher trialkylphosphonium clays had a much larger spacing.

EXAMPLE 2 -- Thermal Stability of Quaternary Tetraalkyl PhosphoniumHectorites

The thermal stability of some of the phosphonium hectorites of Example 1was studied under nitrogen. The rate of weight loss of samples wasexamined between 0 and 900° C. at a heating rate of 6° C. per minute.Methyl trioctyl ammonium hectorite was similarly prepared and tested forcomparison. The results are shown in Table II.

The data show that methyl trioctyl phosphonium hectorite is thermallymuch more stable than its nitrogen analog (Seq. No. 2 vs. 1) It is alsoshown that the decomposition of the octadecyl triethyl phosphoniumhectorite starts at a higher temperature than that of the methyl highertrialkylphosphonium hectorites (Seq. No. 4 vs. 2 and 3). In contrast,changing the length of higher alkyl chains of the methyl trioctylphosphonium derivative has no significant effect on the thermalstability (Seq. No. 2 vs 3).

                                      TABLE II                                    __________________________________________________________________________    THERMOGRAVIMETRIC ANALYSIS.sup.a OF QUATERNARY PHOSPHONIUM                    AND AMMONIUM DERIVATIVES OF REFINED HECTORITE CLAYS                           Sequence                                                                           Chemical Structure                                                                       Decomposition Temp., ° C                                                            Total Weight                                                                         Analysis: Sum of                          No.  of Quaternary Group                                                                      Onset                                                                             Max. Rate                                                                           End                                                                              Loss, %                                                                              C,H and N or P, %                         __________________________________________________________________________    1    (C.sub.8 H.sub.17).sub.3 N.sup.+ CH.sub.3                                                325 405   475                                                                              25     29.2                                      2    (C.sub.8 H.sub.17).sub.3 P.sup.+ CH.sub.3                                                365 480   545                                                                              33     28.3                                      3    (C.sub.16 H.sub.33).sub.3 P.sup.+ CH.sub.3                                               310.sup.b                                                                         510   545                                                                              39     40.3                                      4    C.sub.18 H.sub.37 P.sup.+ (C.sub.2 H.sub.5).sub.3                                        435 505   575                                                                              28     28.6                                      __________________________________________________________________________     .sup.a Rate of Heating: 6° C per minute, S. S. Planchet, Range:        0-900° C, N.sub.2 flow 350 ml per min.                                 .sup.b The main decomposition reaction starts at a higher temperature.   

EXAMPLE 3 -- Preparation of Higher Monoalkyl Trimethyl and TriethylPhosphonium Montmorillonites

The starting clay was a refined sodium montmorillonite supplied by theGeorgia Kaolin Company which is available under the trade name MineralColloid BP. This clay is prepared from Penfield, Wyomingmontmorillonite. The product has a water content of about 10%. Itscomposition corresponds to the following summary formula:

    (Si.sub.7.34 Al.sub.0.66)·(Al.sub.3.18 Fe.sup.3+.sub.0.37 Mg.sub.0.54 O.sub.20 (OH).sub.4 Ca.sub.0.10 K.sub.0.04 Na.sub.0.68

This clay was indicated to have an ion exchange capacity of 90miliequivalents per 100 g dry clay. In the present work, however, it wasfound that it has a minimum ion exchange capacity of 99 me per 100 gtowards tetraalkyl phosphonium chlorides having at least one higheralkyl group. Up to 5% this clay can be easily dispersed in water toyield stable suspensions which can be easily and effectively stirred.Its interplanar repeat distance is 12 A.

In the present example, two higher alkyl trimethyl phosphonium chloridesand four higher alkyl triethyl phosphonium chlorides were reacted withthe above-described sodium montmorillonite to yield the correspondingphosphonium montmorillonites as shown by Table III.

                                      TABLE III                                   __________________________________________________________________________    PREPARATION, INTERPLANAR SPACING AND COMPOSITION OF HIGHER MONO-              ALKYL TRIMETHYL AND TRIETHYL PHOSPHONIUM DERIVATIVES OF                       MONTMORILLONITE (MINERAL COLLOID BP)                                          {[CH.sub.3 (CH.sub.2).sub.0-1 ].sub.2 P.sup.+ C.sub.m H.sub.2n+1 }            Clay.sup.- ; m = 11-20                                                                     Chloride        %, Elemental Composition of Modified Clay           Structure of                                                                            Reactant   X-ray                                                                              Calcd. for 99 me                                 Seq.                                                                             Quaternary Cation                                                                       Used Reaction                                                                            Spacing                                                                            100g. Dry Clay                                                                         Found                                   No.                                                                              on Clay   Moles                                                                              Medium                                                                              .sup.d 001, A                                                                      C  H  P  C  H  P  Cl                             __________________________________________________________________________    1  [(CH.sub.3).sub.3 P.sup.+ C.sub.11 H.sub.23 ]                                           0.018.sup.(a)                                                                      H.sub.2 O  13.80                                                                            2.65                                                                             2.54                                                                             13.42                                                                            2.94                                                                             2.22                                                                             0.05                           2  [(CH.sub.3).sub.3 P.sup.+ C.sub.14 H.sub.29 ]                                           0.0097.sup.(a)                                                                     H.sub.2 O                                                                           18.4 16.20                                                                            3.04                                                                             2.46                                                                             17.20                                                                            3.45                                                                             -- 0.16                           3  [(CH.sub.3).sub.3 P.sup.+ C.sub.20 H.sub.41 ]                                           0.023.sup.(b)                                                                      IPA-H.sub.2 O.sup.(d)                                                               20.8 20.54                                                                            3.75                                                                             2.30                                                                             20.64                                                                            4.14                                                                             2.35                                                                             0.13                           4  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.12 H.sub.25 ]                                    0.027.sup.(a)                                                                      H.sub.2 O                                                                           17.8 16.96                                                                            3.16                                                                             2.43                                                                             16.16                                                                            3.24                                                                             2.33                                                                             0.05                           5  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.16 H.sub.33 ]                                    0.027.sup.(a)                                                                      H.sub.2 O                                                                           21.0 19.86                                                                            3.64                                                                             2.33                                                                             19.48                                                                            3.91                                                                             2.25                                                                             0.10                           6  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.18 H.sub.37 ]                                    0.027.sup.(a)                                                                      H.sub.2 O                                                                           22.1 21.22                                                                            3.86                                                                             2.28                                                                             22.23                                                                            4.24                                                                             2.26                                                                             0.22                           7  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.20 H.sub.41 ]                                    0.023.sup.(c)                                                                      IPA-H.sub.2 O.sup.(d)                                                               21.8 22.50                                                                            4.07                                                                             2.24                                                                             23.52                                                                            4.76                                                                             1.98                                                                             0.19                           __________________________________________________________________________     .sup.(a) About 10% water solution at 50° C.                            .sup.(b) About 3.4% in 1 to 4 ispropanol-water at 50° C.?              .sup.(c) About 10% is 1 to 4 isopropanol-water.                               .sup.(d) Isopropanol-water in a ratio of 1 to 4.                         

In all these reactions, a stable suspension of the sodiummontmorillonite in distilled water or isopropanol-water was used. Theclay concentration was set at about 2% in the reaction mixture. Themajority of the phosphonium chloride reactants was dissolved in warmwater to provide reactant solutions of approximately 10% concentrationat 50° C. In cases of salts having low water solubility, a warm 1 to 4mixture of isopropanol and water was used as a solvent. These lattersolutions were reacted with clays suspended in solvent mixtures ofidentical composition.

All the reactants were carried out at 50° C., by adding 99 me of thephosphonium chloride solution to the well stirred clay suspension atonce. A sudden large increase of viscosity occurred immediately. Inabout 2-3 minutes, the viscosity became manageable. After 30 minutesstirring the mixture was filtered with suction and the cake was washedwith distilled water on the filter funnel. In case of theisopropanol-water mixtures, the identical solvent mixture was used forwashing at first. This was then followed by water. The washing liquidswere employed in three equal volume portions. At the 30 g starting claylevel this volume was 300 ml. The washed, filtered products still hadabout 90% water content. They were dried under 0.1 mm pressure, eitherat room temperature or at 60° C. The dry products were ball milledovernight and then passed through a 200 mesh screen. Thereafter, theywere analyzed and evaluated.

The found carbon, hydrogen and phosphorus content of the products was ingeneral close to the calculated values (Table III). The chlorine contentwas 0.22% or less, indicating that a true ion exchange reaction ratherthan adduct complex formation took place. The formation of the clayderivatives resulted in greatly increased interplanar distances. Thesedistances are directly proportional to the number of carbons in thehigher n-alkyl group of the phosphonium clay substituent. In the rangeexamined, the increase per two additional carbon atoms is in the orderof 1 A. However, this increase is not always the same, it is more of anaverage value. Dependent on their inorganic structure, layered claysseem to prefer to assume structures having certain discrete values. Then-alkyl group being equal (C₂₀), a triethyl phosphonium derivative hadan interplanar distance one A greater than a trimethyl phosphoniumgroup. (Seq. No. 7 vs 3).

EXAMPLE 4 -- Preparation of Higher Monoalkyl Tributyl PhosphoniumMontmorillonites

Higher monoalkyl tri-n-butyl and tri-primary-i-butyl phosphoniumchlorides were reacted with the Mineral Colloid BP clay of the previousexample under similar conditions. A summary of the results is providedin Table IV.

The clay starting material was employed as a 2% aqueous suspension. Thiswas possible since all the phosphonium chlorides of the present serieswere soluble in water. About 10% aqueous chloride solutions were used ateither ambient temperatures or at about 45° C. All the phosphoniumchlorides were again employed at the 99 me per 100 g dry clay treatmentlevel. In the one case, wherein the quaternary salt was impure, acorrespondingly larger quantity was used. The reaction process and theisolation of the products were basically the same as in the previousexample.

As it is shown by Table IV, the found elemental composition of the clayswas in fair agreement with the calculated values. It is felt thatdifferences between the found and calculated values is mostly due to theimpurities in the phosphonium chlorides of the present chlorides. Thesechlorides are viscous liquids very difficult to purify. The chlorinecontent of the products was again low indicating an essentially completeion exchange.

The interplanar spacing was again directly proportional to the length ofthe higher alkyl chain as in the previous example. However, in the caseof the higher alkyl triisobutyl phosphonium clays there was nosignificant change from the C₁₂ to C₁₆ alkyl group. Also in the case ofthe n-C₁₆ alkyl group, the interplanar distance was virtually the samefor the tri-n-butyl and the tri-i-butyl derivatives Seq. No's. In thecase of the n-C₁₂ alkyl compounds, the tri-n-butyl phosphonium clay hada smaller interplanar distance than the tri-i-butyl derivative.

                                      TABLE IV                                    __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION AND COMPOSITION                         OF HIGHER MONOALKYL TRI-n-BUTYL AND TRI-i-BUTYL PHOSPHONIUM                   DERIVATIVES OF MONTMORILLONITE (MINERAL COLLOID BP)                           [(C.sub.4 H.sub.9).sub.4 P.sup.+ C.sub.m H.sub.2m+1 ] Clay.sup.- ; m =        12-18                                                                                       Chloride       Elemental Composition of Modified Clay, %           Structure of                                                                             Reactant                                                                           Reaction                                                                           X-Ray                                                                              Calcd. for 99 me/                                Seq.                                                                             Quaternary Cation                                                                        Used,                                                                              Temp.                                                                              Spacing                                                                            100 g. Dry Clay                                                                        Found                                   No.                                                                              on Clay    Moles                                                                              ° C                                                                         .sup.d 001, A                                                                      C  H  P  C  H  P  Cl                             __________________________________________________________________________    1  [(n-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.12 H.sub.25 ]                                   0.027.sup.a                                                                        Ambient                                                                            20.5 21.22                                                                            3.93                                                                             2.28                                                                             19.61                                                                            3.99                                                                             2.12                                                                             0.07                           2  [(n-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.16 H.sub.33 ]                                   0.022.sup.b                                                                        Ambient                                                                            22.2-22.5                                                                          23.78                                                                            4.28                                                                             2.19                                                                             24.86                                                                            4.77                                                                             2.41                                                                             0.24                           3  [(i-C.sub.4 H.sub.9).sub. 3 P.sup.+ C.sub.12 H.sub.25 ]                                  0.024.sup.c                                                                        45   22.5 21.22                                                                            3.86                                                                             2.28                                                                             21.71                                                                            4.27                                                                             2.20                                                                             0.11                           4  [(i-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.14 H.sub.29 ]                                   0.027.sup.c                                                                        45   22.3 22.52                                                                            4.07                                                                             2.23                                                                             22.62                                                                            4.38                                                                             2.33                                                                             0.12                           5  [(i-C.sub.4 C.sub.9).sub.3 P.sup.+ C.sub.16 H.sub.33 ]                                   0.027.sup.c                                                                        45   22.4 23.05                                                                            4.26                                                                             2.19                                                                             23.85                                                                            4.52                                                                             2.16                                                                             0.08                           6  [(i-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.18 H.sub.37 ]                                   0.135.sup.a                                                                        Ambient                                                                            23.0 24.97                                                                            4.47                                                                             2.16                                                                             25.22                                                                            4.90                                                                             2.09                                                                             0.14                           __________________________________________________________________________     .sup.a About 10% water solution.                                              .sup.b About 15% water solution containing 10% mole excess quaternary due     to impure quaternary.                                                         .sup.c About 10% water solution at 45° C.                         

EXAMPLE 5 -- Preparation of Docosyl Tri-C₁₋₄ - Alkyl PhosphoniumMontmorillonites

Decosyl lower trialkyl phosphonium chlorides were reacted with therefined sodium montmorillonite of the previous example under similarconditions. A summary of the results is provided in Table V.

The clay starting material was again employed at a concentration to givea 2% suspension after the addition of the chloride solution. However,the docosyl trialkyl phosphonium chloride starting reactants of thisexample, in general, showed a lower water solubility than thosepreviously used. Consequently, in this example, both the chlorides andthe clay were dissolved inisopropanol-water mixtures.

On the addition of the chloride solutions to the clay suspensions, thesame immediate reaction took place which was described in the previousexample. The products were also isolated in a manner basically the sameas was used previously.

The found elemental composition of the clays was again close to thetheoretical calculated on the basis of assuming the reaction of all thephosphonium chloride, i.e., 99 me per 100 g dry clay. However, it isnoted that all the found values are slightly higher in contrast to themore unevenly scattered values of the previous example. It is alsointeresting to observe that the chlorine contents found were smaller inthis series than in the earlier.

The interplanar repeat distances of the docosyl trialkyl phosphoniumclays indicate the direct effect of the increasing number of carbonatoms in the n-trialkyl part of the phosphonium moiety on theinterplanar distance. From methyl to n-butyl the increase of thisdistance per carbon is increasing. It is interesting to observe that theinterplanar distance of the tri-isopropyl phosphonium derivative isgreatly increased over that of the corresponding tri-n-propyl compound(Seq. Nos. 3 vs 4). Branching of a small alkyl group apparentlyincreases its effect on the interplanar distance.

                                      TABLE V                                     __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION AND COMPOSITION OF                      DOCOSYL TRI-C.sub.1-4 -ALKYL PHOSPHONIUM DERIVATIVES OF MONT-                 MORILLONITE (MINERAL COLLOID BP)                                              [(C.sub.n H.sub.2n+1).sub.3 P.sup.+ C.sub.22 H.sub.45 ] Clay.sup.- ; n =      1-4                                                                              R Group in                                                                              Chloride      X-Ray                                                                              Elemental Composition of Modified Clay                                        (%)                                           Seq.                                                                             Quaternary Cation                                                                       Reactant                                                                             Reaction                                                                             Spacing                                                                            Calcd for 99 me                                                                        Found                                No.                                                                              C.sub.22 H.sub.45 P.sup.+ R.sub.3                                                       Used, Moles                                                                          Medium .sup.d 001 A                                                                       C  H  P  C  H  P  Cl(Br)                      __________________________________________________________________________    1  CH.sub.3  0.010.sup.(a)                                                                        IPA/H.sub.2 O.sup.(d)                                                                22.4 21.87                                                                            3.96                                                                             2.25                                                                             22.29                                                                            4.34                                                                             2.24                                                                             <0.0%                       2  C.sub.2 H.sub.5                                                                         0.045.sup.(b)                                                                        IPA/H.sub.2 O.sup.(e)                                                                23.0 23.77                                                                            4.27                                                                             2.19                                                                             23.80                                                                            4.51                                                                             2.20                                                                             0.10                        3  n-C.sub.3 H.sub.7                                                                       0.018.sup.(c)                                                                        IPA/H.sub.2 O.sup.(f)                                                                24.2 25.56                                                                            4.57                                                                             2.13                                                                             26.24                                                                            4.93                                                                             2.34                                                                             <0.05                       4  i-C.sub.3 H.sub.7                                                                       0.018.sup.(c)                                                                        IPA/H.sub.2 O.sup.(f)                                                                25.7 25.56                                                                            4.57                                                                             2.13                                                                             26.42                                                                            5.01                                                                             2.23                                                                             <0.03                       5  n-C.sub.4 H.sub.9                                                                       0.018.sup.(c)                                                                        IPA/H.sub.2 O.sup.(f)                                                                26.0 27.24                                                                            4.85                                                                             2.07                                                                             28.05                                                                            5.18                                                                             2.29                                                                             <0.03                       6  i-C.sub.4 H.sub.9                                                                        0.135.sup.(a,g)                                                                     IPA/H.sub.2 O.sup.(d)                                                                     27.24                                                                            4.85                                                                             2.07                                                                             26.67                                                                            5.05                                                                             2.02                                                                             (0.63)                      Miliequivalent quaternary per 100 g starting dry clay.                        __________________________________________________________________________     .sup.(a) About 2.7% in 1 to 3 isopropanol-water at 53° C.              .sup.(b) About 6% in about 1 to 4 isopropanol-water.                          .sup.(c) About 10% in 1 to 5 isopropanol-water.                               .sup.(d) Isopropanol-water in a ratio of 1 to 3.                              .sup.(e) Isopropanol-water in a ratio of 1 to 4.                              .sup.(f) Isopropanol-water in a ratio of 1 to 5.                              .sup.(g) Quaternary bromide reactant was used.                           

EXAMPLE 6 -- Preparation of Higher Dialkyl Dimethyl and DiethylPhosphonium Montmorillonites

Higher dialkyl dimethyl and diethyl phosphonium chlorides were reactedwith the sodium montmorillonite of the previous example in the usualmanner. The results are summarized in Table VI.

The clay starting material was again used at the 2% concentration level.The solvent media, i.e., water or isopropanolic water were identical forthe clay and the phosphonium chloride reactants. The phosphoniumchloride solution of 10 to 37% concentration was added all at once tothe 2% clay suspension at 50° C. The treatment level was 99 me chlorideper 100 g vacuum dried clay. On the addition of the chloride animmediate reaction occurred in the usual manner. For the isolation ofthe higher dialkyl dimethyl and diethyl phosphonium montmorilloniteproducts basically the previously used procedure was employed.

As it is shown by the analytical data of Table VI, the found elementalcomposition of the products is in good agreement with their calculatedvalues. It is noted that the three higher dialkyl dimethylmontmorillonites had only trace amounts of chlorine. This indicates thatthere was no excess, unconverted phosphonium chloride reactant but anessentially complete ion exchange.

The interplanar spacing of the quaternary higher dialkyl phosphoniumclays of Table VI is in general much larger than that of the quaternaryhigher monoalkyl phosphonium clays in Table III. For example, thespacing of dioctadecyl diethyl phosphonium montmorillonite of Table VI,Seq. No. 4 is 28.4° A while that of the monooctadecyl triethylphosphonium montmorillonite of Table III, Seq. No. 5 is 22.1° A. Withinthe higher dialkyl series of Table VI, the spacing is generally directlyproprotional to the length of the alkyl chains. However, there is noincrease in spacing from the dioctyl to the didecyl derivative (Seq.Nos. 1,2).

                                      TABLE VI                                    __________________________________________________________________________    PREPARATION INTERPLANAR SPACING AND COMPOSITION OF HIGHER DIALKYL             DIMETHYL AND DIETHYL PHOSPHONIUM DERIVATIVES OF MONTMORILLONITE               (MINERAL COLLOID BP)                                                          [(C.sub.r H.sub.2r+1).sub.2 P.sup.+ (CH.sub.2).sub.0-1 CH.sub.3 ]             Clay.sup.- ; r = 8-18                                                                                        Elemental Composition of Modified Clay                                        (%)                                               Structure of                                                                             Chloride    X-Ray                                                                               Calc for 99 me/                               Seq.                                                                             Quaternary Cation                                                                        Reactant                                                                            Reaction                                                                            Spacing                                                                            100 g Dry Clay                                                                          Found                                No.                                                                              on Clay    Used, Moles                                                                         Medium                                                                              .sup.d 001, A                                                                      C  H  P   C  H  P  Cl                          __________________________________________________________________________    1  [(CH.sub.3).sub.2 P.sup.+ (C.sub.8 H.sub.17).sub.2 ]                                     0.020.sup.(a)                                                                       H.sub.2 O                                                                           20.5 16.96                                                                            3.16                                                                             2.43                                                                              20.38                                                                            4.12                                                                             2.53                                                                             0.02                        2  [(CH.sub.3).sub.2 P.sup.+ (C.sub.10 H.sub.21).sub.2 ]                                    0.020.sup.(b)                                                                       IPA/H.sub.2 O.sup.(e)                                                               20.3 19.86                                                                            3.64                                                                             2.33                                                                              20.28                                                                            4.02                                                                             2.51                                                                             0.02                        3  [(CH.sub.3).sub.2 P.sup. + (C.sub.12 H.sub.25).sub.2 ]                                   0.027.sup.(c)                                                                       IPA/H.sub.2 O.sup.(f)                                                               22.6-                                                                              22.52                                                                            4.07                                                                             2.22                                                                              21.53                                                                            4.30                                                                             2.13                                                                             Nil                                                   23.4                                                4  [(C.sub.2 H.sub.5).sub.2 P.sup.+ (C.sub.18 H.sub.37).sub.2 ]                             0.014.sup.(d)                                                                       IPA/H.sub.2 O.sup.(g)                                                               28.4*                                                                              30.35                                                                            5.35                                                                             1.96                                                                              30.40                                                                            5.88                                                                             2.00                                                                             0.17                        __________________________________________________________________________     .sup.(a) About 10% water solution at room temperature.                        .sup.(b) About 10% at ambient temperature.                                    .sup.(c) About 37% at ambient temperature.                                    .sup.(d) About 18% at 70° C.                                           .sup.(e) Isopropanol-water in ratio of 1 to 3.                                .sup.(f) About 2.3% isopropanol in water.                                     .sup.(g) Isopropanol-water in a ratio of 1 to 4.                         

EXAMPLE 7 -- Preparation of Quaternary Higher Trialkyl PhosphoniumMontmorillonites

To a well stirred, stable 2% clay suspension, containing 30 g. ofMineral Colloid BP of 10% water content from Georgia Kaolin Co., in awater-isopropanol medium at 50° C., 99 miliequivalent per 100 g. dryclay (i.e., 0.027 mole) of quaternary chloride dissolved in an identicalwaterisopropanol medium (9% quaternary chloride) at approximately 45-50°C. was added all at once. The isopropanol in water concentration waskept at the minimum required to prepare approximately 9% solutions ofthe quaternary chlorides at 45-50° C. This concentration was 20% in thepreparation of clays having Sequence Numbers 1 and 3, 33% for Seq. Nos.2, 4, 5 and 9 and 50% for Seq. Nos. 6 and 7 in Table VII. In general, asthe carbon number of the higher alkyl groups increased, theconcentration of the isopropanol had to be increased as well. In thecase of the trihexadecyl phosphonium chlorides of Table VIII (Seq. Nos.3 and 4,) a one to one mixture of isopropanol and water was used.

                                      TABLE VII                                   __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION AND COMPOSITION OF QUATERNARY           TRIHEXYL, TRIOCTYL                                                            AND TRIDECYL PHOSPHONIUM DERIVATIVES OF MONTMORILLONITE CLAY (MINERAL         COLLOID BP)                                                                                                       Elemental Composition of Modified                                             Clay (%)                                     Structure of  Chloride     X-Ray Calc for 99 me/                           Seq.                                                                             Quaternary Cation                                                                           Reactant                                                                             Reaction                                                                            Spacing                                                                             100 g Dry Clay                                                                           Found                          No.                                                                              on Clay       Used, Moles                                                                          Medium                                                                              .sup.d 001,A                                                                        C   H  P   C   H   P   Cl                 __________________________________________________________________________    1  [(C.sub.6 H.sub.13).sub.3 P.sup.+ CH.sub.3 ]                                                0.027.sup.(a)                                                                        IPA/H.sub.2 O.sup.(e)                                                               17.8  17.71                                                                             3.29                                                                             2.40                                                                              17.63                                                                             3.60                                                                              2.25                                                                              0.04               2  [(C.sub.8 H.sub.17).sub.3 P.sup.+ CH.sub.3 ]                                                0.027.sup.(b)                                                                        IPA/H.sub.2 O.sup.(f)                                                               22.1-22.6                                                                           21.88                                                                             3.97                                                                             2.26                                                                              21.63                                                                             4.35                                                                              2.28                                                                              0.08               3  [(C.sub.8 H.sub.17).sub.3 P.sup.+ C.sub.2 H.sub.5 ]                                         0.027.sup.(a)                                                                        IPA/H.sub.2 O.sup.(e)                                                               22.2  22.52                                                                             4.01                                                                             2.23                                                                              22.61                                                                             4.48                                                                              2.24                                                                              0.13               4  [ (C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.3 H.sub.7 ]                                      0.027.sup.(b)                                                                        IPA/H.sub.2 O.sup.(f)                                                               22.0  23.15                                                                             4.18                                                                             2.21                                                                              23.21                                                                             4.60                                                                              2.27                                                                              0.01               5  [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.4 H.sub.9 ]                                       0.027.sup.(b)                                                                        IPA/H.sub.2 O.sup.(f)                                                               22.5  23.77                                                                             4.28                                                                             2.19                                                                              23.93                                                                             4.67                                                                              2.18                                                                              0.09               6  [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.5 H.sub.11 ]                                      0.027.sup.(c)                                                                        IPA/H.sub.2 O.sup.(g)                                                               22.6  24.37                                                                             4.38                                                                             2.17                                                                              20.75                                                                             4.20                                                                              1.93                                                                              0.02               7  [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.6 H.sub.13 ]                                      0.027.sup.(c)                                                                        IPA/H.sub.2 O.sup.(g)                                                               22.4  24.97                                                                             4.47                                                                             2.15                                                                              20.46                                                                             4.16                                                                              1.78                                                                              0.04                   ##STR5##     0.027.sup.(c)                                                                        IPA/H.sub.2 O.sup.(g)                                                               22.4  25.70                                                                             4.04                                                                             2.14                                                                              23.16                                                                             4.10                                                                              1.76                                                                              0.06               9  [(C.sub.10 H.sub.21).sub.3 P.sup.+ CH.sub.3 ]                                               0.027.sup.(d)                                                                        IPA/H.sub.2 O.sup.(g)                                                               25.2  25.56                                                                             4.57                                                                             2.13                                                                              25.79                                                                             4.99                                                                              2.09                                                                              0.06               __________________________________________________________________________     .sup.(a) About 10% solution at 40° C.                                  .sup.(b) About 9% at 50° C.                                            .sup.(c) About 10% solution at 50° C.                                  .sup.(d) About 6% solution at 50° C.                                   .sup.(e) Isopropanol-water at 1 to 5 ratio                                    .sup.(f) Isopropanol-water at 1 to 3 ratio                                    .sup.(g) Isopropanol-water at 1 to 2 ratio                               

                                      TABLE VIII                                  __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION AND COMPOSITION OF QUATERNARY           TRINONYL AND                                                                  TRIHEXADECYL PHOSPHONIUM DERIVATIVES OF MONTMORILLONITE CLAY (MINERAL         COLLOID BP)                                                                                                          Elemental Composition of Modified                                             Clay (%)                                  Structure of   Chloride                                                                              i-Propanol                                                                           X-ray Calc for 99 me/                        Seq.                                                                             Quaternary Cation                                                                            Reactant                                                                              Water  Spacing                                                                             100 g dry clay                                                                          Found                        No.                                                                              on Clay        Used, Moles                                                                           Ratio.sup.c                                                                          001 A C  H   P  C  H   P   Cl                __________________________________________________________________________    1  (C.sub.9 H.sub.19).sub.3 P.sup.+ CH.sub.3                                                    0.0180.sup.a                                                                          1/3          23.77                                                                            4.28                                                                              2.19                                                                             23.91                                                                            4.70                                                                              2.21                                                                              0.09              2  (C.sub.9 H.sub.19).sub.3 P.sup.+ C.sub.2 H.sub.5                                             0.0135.sup.a                                                                          1/4    23.5  24.37                                                                            4.38                                                                              2.17                                                                             24.45                                                                            4.83                                                                              2.38                                                                              0.11              3  (C.sub.16 H.sub.33).sub.3 P.sup.+ C.sub.2 H.sub.5                                            0.0300.sup.b                                                                          1/1    31.5  34.84                                                                            6.08                                                                              1.79                                                                             35.95                                                                            6.57                                                                              2.19                                                                              0.24              4  (C.sub.16 H.sub.33).sub.3 P.sup.+ CH.sub.2 CH(CH.sub.3).sub.2                                0.2700.sup.b                                                                          1/1    34.4  35.65                                                                            6.21                                                                              1.76                                                                             35.92                                                                            6.42                                                                              1.82                                                                              0.08              __________________________________________________________________________     .sup.a About 10% solution at 40°.                                      .sup.b About 5% solution at 40°.                                       .sup.c The concentration of the clay reactant in the final                    isopropanol-water medium is about 2%.                                    

Upon mixing the reactants, a large temporary increase of the reactionmixture viscosity was observed, followed by a gradual breakdown of thisincreased viscosity. The reaction mixture was stirred at 50° C. for 30minutes and then immediately filtered with suction. The filter-cake waswashed two times with ten-fold quantities of the isopropanolwatermixture used as the reaction medium and once with a similar quantity ofdistilled water. Thereafter, the product was dried in vacuo (0.1 mm) at60° C. and ball-milled for 18 hours. The ball-milled product wassubmitted for X-ray and elemental analysis; it was then sieved through a200 mesh screen and subjected to testing.

The found elemental compositions of the phosphonium clay products are inexcellent agreement with the calculated values in all cases but two(Seq. Nos. 6 and 7). Particularly encouraging are the low chlorinevalues which are indicative of complete ion exchange at the relativelyhigh 99 milliequivalent quaternary chloride per 100 g clay treatmentlevel. The low phosphonium contents reported for both the pentyl andhexyl trioctyl phosphonium clay products (Seq. Nos. 6 and 7) have beensubstantiated and are probably due to a low quaternary content of thestarting chlorides.

The interplanar spacings of the quaternary higher trialkyl methylphosphonium clays of Table VII is much higher than those of thecorresponding higher dialkyl analogs of Table VI. For example, thespacings of the trioctyl and tridecyl clays of Table VII, Seq. Nos. 2and 10, were much larger than those of the dioctyl and didecyl clays ofTable VI, Seq. Nos. 1 and 2.

It is interesting that the interplanar spacing of all the quaternarytrioctyl phosphonium clays from the methyl through the hexyl derivative(Seq. Nos. 2-7) is essentially the same (22.0-22.6 A). Even, the benzyltrioctyl phosphonium clay has a similar spacing (Seq. No. 8). Incontrast, decreasing the lengths of the higher trialkyl substituentsfrom eight carbons to six carbons results in a largely decreased spacing(4.5 A, Seq. No. 1 vs 2). Increasing the length of the trialkyl groupfrom eight carbons to ten carbons also results in a substantiallyincreased spacing (2.9 A, Seq. No. 2 vs 9). However, it is noted thatthis increase is down to almost half the value observed for theanalogous 2 carbon change from the trihexyl to the trioctyl group.

The above data on the interplanar spacing of quaternary higher trialkylphosphonium montmorillonites can be explained by assuming aperpendicular orientation of the higher alkyl groups relative to thesurface of the aluminosilicate layers.

The data indicate that a definite perpendicular orientation of the threehigher n-alkyl groups relative to the surface of the aluminosilicatelayers does not occur until their carbon number is above 6 per chain.Furthermore, it seems that the accommodation of the fourth alkyl groupof these quaternary derivatives in the C₁ to C₆ range without affectingthe interplanar spacing is best explained by an orientation parallel tothe plane. For example, in the case of the hexyl trioctyl phosphoniummontmorillonite FIG. 1 indicates the proposed orientation.

The interplanar spacings of the two quaternary trihexadecyl phosphoniumclays of Table III are unexpectedly low and different. The low valuescan be explained, however, if a non-perpendicular orientation of thehexadecyl groups is assumed. The significant difference between theinterplanar spacings of the ethyl and isobutyl trihexadecyl phosphoniumclays can be apparently attributed to alkyl branching. The branches ofthe isobutyl substituent leads to a considerable increase of interplanarspacing because it is not oriented parallel to the surface of thealuminosilicate surface.

This hypothesis also explains the adverse effect of increasing thenumber of carbons of the fourth alkyl group on the gelling ability ofsuch clays as described in Example 23.

EXAMPLE 8 -- Preparation of Unsymmetrically Substituted Higher MonoalkylPhosphonium Montmorillonites

According to the general procedure described in the previous example,the unsymmetricaal low trialkyl substituted high monoalkyl phosphoniummontmorillonites of Table IX were prepared. Most of the preparationswere carried out in water media, since the corresponding phosphoniumchloride starting materials were sufficiently water soluble. One of thephosphoium salts had a higher alkyl substituent with varying even numberof carbon atoms in the 24 to 28 range. As it is indicated by the formulaof the quaternary cation, the average number of carbon atoms was 27(Seq. No. 2).

                                      TABLE IX                                    __________________________________________________________________________    INTERPLANAR SPACING OF 001 REFLECTION AND COMPOSITION Of QUATERNARY           UNSYMMETRICALLY                                                               SUBSTITUTED LOW TRIALKYL HIGH MONOALKYL PHOSPHONIUM DERIVATIVES               OF MONTMORILLONITE CLAY (MINERAL COLLOID BP)                                                      Conc. Chloride                                                                           i-   X-ray                                                                              Elemental Composition of                                                      Modified Clay, %                        Structure of     of Clay                                                                             Reactant                                                                           Propanol                                                                           Spacing                                                                            Calc. for 100 me/                    Seq.                                                                             Quaternary Cation                                                                              in Medium                                                                           Used,                                                                              to Water                                                                           001  100 g dry clay                                                                          Found                      No.                                                                              on Clay          (%)   Moles                                                                              Ratio.sup.a                                                                        A    C  H   P  C  H  P  Cl                __________________________________________________________________________    1  (C.sub.2 H.sub.5).sub.2 P.sup.+ (CH.sub.3)C.sub.18 H.sub.37                                    3     0.150.sup.b                                                                        0/1  21.6 20.54                                                                            3.75                                                                              2.30                                                                             20.80                                                                            3.75                                                                             2.20                                                                             0.18              2  (C.sub.2 H.sub.5).sub.2 P.sup.+ (CH.sub.3)C.sub.27 H.sub.54                                    2     0.027.sup.c                                                                         1/10                                                                              24.6 26.69                                                                            4.75                                                                              2.08                                                                             25.41                                                                            4.85                                                                             2.01                                                                             0.26              3  (C.sub.2 H.sub.5).sub.2 P.sup.+ (CH.sub.2 CH═CH.sub.2)C.sub.18            H.sub.37         2     0.027.sup. d                                                                       0/1  23.2                                      4  (i-C.sub.4 H.sub.9).sub.2 P.sup.+ (C.sub.2 H.sub.5)C.sub.12 H.sub.25                           2     0.027.sup.d                                                                        0/1  21.3 19.86                                                                            3.64                                                                              2.33                                                                             20.94                                                                            4.10                                                                             2.35                                                                             0.05              5  (i-C.sub.4 H.sub.9).sub.2 P.sup.+ (C.sub.2 H.sub.5)C.sub.16 H.sub.33                           2     0.054.sup.d                                                                        0/1  22.6 22.53                                                                            4.22                                                                              2.24                                                                             23.52                                                                            4.58                                                                             2.18                                                                             0.05              6  (i-C.sub.4 H.sub.9).sub.2 P.sup.+ (CH.sub.2 CH═CH.sub.2)C.sub.12          H.sub.25         2     0.018.sup.d                                                                         1/10     20.57                                                                            3.60                                                                              2.31                                                                             20.73                                                                            4.01                                                                             2.33                                                                             0.31              __________________________________________________________________________     .sup.a The isopropanol water ratio of the clay suspension and phosphonium     salt solution reactants is generally the same. If the solution has a          different solvent ratio it is specificaly stated so in a proper footnote.     .sup.b About 7% solution at 50°.                                       .sup.c About 10% solution in 2 to 1 isopropanol water at 50°.          .sup.d About 10% solution.                                               

The elemental and X-ray analysis of the products indicated theirstructure. The interplanar distance of the quaternary diethyl octadecylphosphonium derivatives (Seq. Nos. 1 and 3) as expected showed littledependence on the third low alkyl group as shown by a comparison withthe value for the corresponding triethyl octadecyl phosphonium clay ofTable III, Seq. No. 6. Similarly, the interplanar distances of the twoethyl diisobutyl high monoalkyl phosphonium clays (Seq. Nos. 4 and 5)are comparable to those of the corresponding triisobutyl high monoalkylphosphonium clays (Table V, Seq. Nos. 3 and 5).

EXAMPLE 9 -- Preparation of Unsymmetrically Substituted Higher DialkylPhosphonium Montmorillonites

To a stirred 2% suspension of 30 g of the sodium montmorillonite in aone to five mixture of isopropanol and water, 0.027 mole of theappropriate phosphonium chloride was added as a 10% solution in asolvent mixture of the same composition. As usual, both the claysuspension and the phosphonium salt were at about 50° C. when mixed. Aninstantaneous reaction occurred in the usual manner. The products wereisolated following the general procedure of the previous examples. Theanalyses of the dry products indicated that the expected phosphoniumsubstitution of the clay occurred as shown by Table X.

                                      TABLE X                                     __________________________________________________________________________    QUATERNARY UNSYMMETRICALLY SUBSTITUTED LOW DIALKYL HIGH                       DIALKYL PHOSPHONIUM DERIVATIVES OF MONTMORILLONITE CLAY                       (MINERAL COLLOID BP)                                                                               Elemental Composition of Modified Clay, %                   Structure of      Calcd. for 100 me/                                       Seq.                                                                             Quaternary        100 g Dry Clay                                                                          Found                                          No.                                                                              Cation on Clay    C   H  P  C  H  P  Cl                                    __________________________________________________________________________    1  (C.sub.12 H.sub.25).sub.12 P.sup.+ (C.sub.2 H.sub.5)i-C.sub. 4                H.sub.9           24.97                                                                             4.47                                                                             2.15                                                                             26.14                                                                            5.10                                                                             2.31                                                                             0.09                                  2  (C.sub.16 H.sub.33).sub.2 P.sup.+ (C.sub.2 H.sub.5)i-C.sub.                                     25.59ub.9                                                                         4.43                                                                             2.13                                                                             26.51                                                                            4.91                                                                             2.20                                                                             0.25                                  3  (C.sub.12 H.sub.25).sub.2 P.sup.+ (CH.sub.2 CH═CH.sub.2)i-C.sub. 4        H.sub.9           29.35                                                                             5.19                                                                             1.99                                                                             30.29                                                                            5.77                                                                             1.91                                                                             0.11                                  __________________________________________________________________________

example 11 -- preparation of Vinylbenzyl Triethyl PhosphoniumMontmorillonite

45 g montmorillonite clay is dispersed in a 2 to 1 mixture ofwater-isopropanol at 45° C. to yield a 3% suspension. To the wellstirred suspension, a 15% solution of 13.55 g (0.05 mole) of vinylbenzyltriethyl phosphonium chloride is added at 45° C. at once. This resultedin an immediate tremendous thickening of the mixture. A few minutesafter the addition, the viscosity decreased. Stirring of the reactionmixture was continued for 45 minutes. Thereafter, the product wasisolated in the usual manner.

Elemental analysis: Calculated for 100 miliequivalent phosphonium group,##STR6## per 100 g dry starting clay: C, 13.62; H, 1.83; P, 2.34; Found:C, 12.02; H, 2.19; P, 2.25, Cl, 0.07. Interplanar spacing of 001Reflection by X-Ray: 15.7° A.

EXAMPLE 12 -- Preparation of Tetraethyl Phosphonium Montmorillonite Clay

To a stirred aqueous suspension of 22.2 g sodium montmorillonite (MCBP)a 5% aqueous solution of 3.65 g (0.02) tetraethyl phosphonium chloridewas added at 50° C. so as to obtain a reaction mixture having a 2%concentration of the starting clays. A thickening of the mixtureoccurred within a few minutes rather than seconds after the addition.After 30 minutes stirring the product was isolated as usual.

Using a 1% aqueous suspension of sodium hectorite, tetraethylphosphonium hectorite was prepared in a similar manner.

EXAMPLE 13 -- Preparation of Tetrabutyl Phosphonium Montmorillonite

To a stirred aqueous suspension of 60 g refined sodium montmorillonite(MCBP) at 50° C., a 10% aqueous solution of 15.93 g (0.054 mole) oftetra-n-butyl phosphonium chloride was added all at once to yield areaction mixture of 2% starting clay concentration. On mixing animmediate thickening and then in a few minutes the formation of largecoarse tetrabutyl phosphonium clay particles occurred. After 30 minutesstirring, the product was isolated in the usual manner.

Elemental analysis: Calculated for 99 me (C₄ H₉)₄ P⁺ group per 100 g dryclay: C, 15.42; H, 2.91; P, 2.49. Found: C, 13.24; H, 3.06; P, 2.09.

The same product was prepared in a similar manner, starting with 60 gclay and 20.43 g (0.054 mole) of tetrabutyl phosphonium acetate-aceticacid adduct, [(n-C₄ H₉)₄ P⁺ ]CH₃ CO₂ ⁻ ·CH₃ CO₂ H.

EXAMPLE 14 -- Preparation of Decosyl Trimethyl Phosphonium Laponite XLGSynthetic Clay

Laponite XLG from Pfizer is a pure fluorine free synthetic inorganicclay. It is prepared by the removal of electrolyte impurities fromLaponite CP which was described by B. S. Neumann and K. G. Sansom in theJournal of the Society of Cosmetic Chemists in Volume 21, pages 237 to258 in 1970. Its formula is [Si₈ Mg₅.1 Li₀.6 H₄.6 O₂₄ ]⁰.6 Na₀.6. Itscation exchange capacity, as determined using ammonium acetate, is 79miliequivalents per 100 g.

A clear, viscous colloidal suspension of 25 g Laponite XLG in 700 ml of2 to 1 water-isopropanol mixture was prepared by stirring for one hourat 50° C. Then a 45° C. solution of 8.4 g. (0.02 m) of docosyl trimethylphosphonium chloride in 940 ml of the same solvent mixture was added toit fast at 50° C. while stirring. On addition, a moderate degree offurther thickening of the mixture occurred. This thickening disappearedin a few minutes and small particles of the white product appeared.After 30 minutes stirring, the phosphonium laponite product was isolatedand dried in the usual manner.

Elemental analysis: Calculated for 79 me C₂₂ H₂₅ P⁺ (C₂ H₅)₃ group per100 g starting laponite clay: C, 18.62; H, 3.38; P, 1.92. Found: C,19.92; H, 4.10; P, 1.98; Cl < 0.02.

A similar experiment was carried with docosyl trimethyl phosphoniumchloride, using it at the 100 miliequivalent per 100 g laponitetreatment level to produce an organic clay having a higher percentage ofphosphonium moieties.

Elemental analysis: Calculated for 100 me salt per 100 g clay: C, 22.03;H, 3.99; P, 2.28. Found: C, 23.51; H, 4.81; P, 2.39; Cl, 0.09.

EXAMPLE 15 -- Preparation of Docosyl Triethyl Phosphonium Laponite XLGSynthetic Clay

A colloidal suspension of 24.9 g Laponite XLG in 1120 ml 20%isopropanolic water was prepared in 75 minutes stirring at 50°. To thesuspension a 10% solution of 9.13g (0.0197 mole) of docosyl triethylphosphonium chloride in the same medium was added at a fast rate. Theaddition resulted in a stronger gel. However, during continued stirringfor 30 minutes, the viscosity decreased. This mixture was then filteredby suction at a slow rate because of its gel-like character. After theusual washing, the white solid product was isolated by drying in vacuo.

Elemental analysis: Calculated for 79 me C₂₂ H₄₅ P⁺ (C₂ H₅)₃ per 100 glaponite: C, 20.13; H, 3.62; P, 1.86. Found: C, 21.50; H, 4.18; P, 1.98.

EXAMPLE 16 -- Preparation of Docosyl Triethyl Phosphonium Laponite BSynthetic Clay

Laponite B from Pfizer is a synthetic clay closely approximating thechemical composition of natural Hectorite. Its percentage compositionis: SiO₂, 55.9; MgO, 26.7; Li₂ O, 1.9; F, 8.3; Na₂ O, 4.3; Fe₂ O₃, 0.04;CaO, 0.10; SO₃, 0.05; CO₂, 0.24; H₂ O (Structural), 3.60. Its cationexchange capacity is in the range of 80 to 110 me per 100 g.

To a hazy, viscous colloidal suspension of 19.7 g Laponite B in 872 ml20% isopropanol in water mixture at 50° C., a 10% solution of 9.13 g(0.0197 mol) of docosyl triethyl phosphonium chloride in the samesolvent medium was added at a fast rate. An immediate reaction wasindicated by the turn of the mixture to a white suspension. However,there was no great change in viscosity of the mixture at any time duringthe reaction. After 30 minutes stirring at 50° C., the viscous mixturewas filtered with suction with difficulty. The white, solid product wasthen washed and dried in the usual manner.

Elemental analysis: Calculated for 100 miliequivalent C₂₂ H₄₅ P⁺ (C₂H₅)₃ per 100 g clay: C, 23.94; H, 4.31; P, 2.21. Found: C, 24.28; H,4.25; P, 2.27; Cl, 0.33.

EXAMPLE 17 -- Preparation of 4-Vinylbenzyl Triethyl PhosphoniumKaolinite

The kaolinite used in this reaction is a hydrated aluminum silicate. Itis a white china clay processed by fractional centrifugation to have amedian particle size of 0.55 microns. A 20% aqueous slurry of this clayhas a pH of 4.2 to 5.2. A 70% slurry has a Brookfield viscosity of 430centipoise at 10 rpm. Its oil adsorption is 42% by the Garden Colmantechnique.

Elemental composition, %: Al₂ O₃, 38.38; SiO₂ (combined), 45.30; H₂ O(combined, ignition loss at 950° C.), 13.97; Fe₂ O₃, 0.30; TiO₂, 1.44;CaO, 0.05; MgO, 0.25; Na₂ O, 0.27, K₂ O, 0.04.

As a dispersant for the hydrite in water, either sodiumhexametaphosphate and sodium carbonate from Mill Chem (MC) orethylenediamine (EDA) was used. The general procedure for the kaolindispersion and reaction with the phosphonium salt was the following.

Using an Osterizer, high speed mixer 300 ml water was blended with theproper amounts of one of the above dispersants. Then with continuedstirring, 250 g Hydrite 10 was added. After the addition, stirring wascontinued at a high speed for 5 minutes. The resulting kaolin dispersionwas transferred into a beaker, using distilled water to wash theOsterizer and to dilute the dispersion to a 10-15% solids in waterlevel. The contents of the beaker were then mixed with a mechanicalstirrer for 3-5 minutes and checked for pH and dispersion quality. ThepH of the Calgon dispersions was 6.0 while that of the EDA dispersionswas 9.8.

To the above dispersion, either 3.125 g (1.25% salt, i.e. 0.15%phosphorus) or 6.25 g (2.5% salt, i.e. 0.3% phosphorus) of 4-vinylbenzyltriethyl phosphonium chloride salt was added with stirring. Stirring wascontinued for several minutes and the pH monitored. Then the mixture waseither kept at room temperature for 10 minutes or slowly heated to 65°C. and held there for 10 minutes while stirring. The solids were thenfiltered with suction and dried at 100°-110° C. to provide the products.

The results show that using 0.15% phosphorus in the form of thephosphonium salt reactant, a complete reaction occurs with the sodiumhexametaphosphate dispersed aqueous kaolinite independent of thereaction temperature. Doubling the amount of phosphonium reactant doesnot increase the 0.15% phosphorus content of the product. Usingethylenediamine instead of sodium hexametaphosphate reduces thephosphorus content to about 0.1% regardless of the reactant ratio andreaction temperature and the bisicity of the reaction mixture.

EXAMPLE 18 -- Preparation of 14-Diphenylphosphinotetradecyl TriethylPhosphonium Montmorillonite and Its Complexing with 1,5-CyclooctadieneRhodium Chloride

To a stirred nitrogenated 0.85% suspension of 18.5 g dry (20.5g wet)MCBP in 50% aqueous isopropanol, an 8.5% solution under nitrogen of 10g(0.019 m) of 14-diphenylphosphinotetradecyl triethyl phosphoniumchloride, also in 50% aqueous isopropanol was added during the course ofa minute. Immediate reaction was indicated by a typical thickening ofthe mixture. After 30 minutes additional stirring, the product wasfiltered off with suction, washed and dried at 60° in the usual manner.

The above phosphinoalkyl phosphonium montmorillonite was ball-milled andscreened using a 200 mesh screen. Of the screened phosphonium clay, 16.3g was dispersed with stirring under nitrogen in a 0.25% benzene solutionof 1.36 g (0.01 m) of 1,5-cyclooctadiene rhodium chloride dimer. Astable suspension resulted which was filtered with suction and washedthree times with 50 ml nitrogenated benzene to provide the bright yellowsolid clay complex product.

After drying overnight at room temperature at 0.1 m m. the product wasanalyzed for rhodium and phosphorus. The percentage values found wereRh, 1.94; P, 2.77. These values show that almost one atom rhodium wascomplexed per two phosphine moieties. The degree of rhodium removal fromthe benzene by complexation was about 60%.

EXAMPLE 19 -- Preparation of bis 3-Hydroxypropyl Octadecyl PrimaryIsobutyl Phosphonium Montmorillonite

To a stirred nitrogenated 2.25% aqueous suspension of 25 g (0.0225 moleequivalent) MCBP at 50°, at 10% aqueous solution of 11.1g (0.0225 mole)3-hydroxypropyl octadecyl primary isobutyl phosphonium chloride, also at50°, is added all at once. A thickening of the reaction mixture and aswelling of the clay occurred within a minute of the addition. Duringthe subsequent 30 minute stirring, the viscosity decreased. Thereafter,the mixture was promptly filtered with suction and washed with three 250ml portions of water in 15 minutes. The filter cake was then dried for72 hours at room temperature under 0.1 mm pressure to provide the dryproduct in a quantitative yield.

The ball milled product of less than 200 mesh size swells in styrene andis an effective gellant for alkyd resins.

EXAMPLE 20 -- Preparation of bis-3-Hydroxypropyl Docosyl PrimaryIsobutyl Phosphonium Montmorillonite

Bis-3-hydroxypropyl docosyl primary isobutyl phosphonium chloride(12.2g, 0.0225 m) was reacted with 25 g (0.0225 mole equivalent) MCBP inthe manner described in the previous example to yield the correspondingphosphonium montmorillonite gellant.

EXAMPLE 21 -- Preparation of Bis-3-Dimethylaminopropyl Dodecyl PrimaryIsobutyl Phosphonium Montmorillonite

Bis-3-dimethylaminopropyl dodecyl primary isobutyl phosphonium chloride(10.5g, 0.0225 m) was reacted with 25 g (0.0225 mole equivalent) MCBP inthe manner described in Example 18 to yield the correspondingphosphonium montmorillonite.

EXAMPLE 22 -- Preparation of Tris-cyanoethyl Dodecyl PhosphoniumMontmorillonite

Tris-cyanoethyl dodecyl phosphonium bromide (10g, 0.0225 m) was reactedwith 25g (0.0225 mole equivalent) MCBP in the manner described inExample 18 to yield the corresponding phosphonium montmorillonite.

THE METHODS USED TO DETERMINE GELLING ABILITY

All the gel test methods give somewhat different results if organicclays of various particle size are used. Therefore, the dry, ball milledclays were all passed through a 200 mesh screen before testing.

The Styrene Swelling Test

A two gram organic clay sample was slowly added using a spatula to 100ml polymerization grade styrene. The styrene was contained in a 100 mlmeasuring cylinder of about 2.5 cm diameter. On the addition of the claygelling agents, a spontaneous gelling occurred. The resulting gel volumeof the clays was severalfold of the original by the time they fell tothe bottom of the cylinder. The volume of the resulting bottom gel"phase" was read after 15 minutes, 2 hours and 24 hours.

The Toluene Gel Strength Test

To 294 g toluene placed into a Waring blender, 6 g of tetraalkylphosphonium clay is added in 45 seconds while it is stirred at a rate ofabout 10,000 rpm (transformer setting 25). The resulting mixture is thenstirred at 15,000 rpm for 90 seconds (Transformer setting 100). Thestirring rate is then reduced to 13,000 and 2.3 ml polar additive,consisting of 95% commercial (i.e., 99%) methanol and 5% distilled wateris added over 30 seconds. The speed is then again increased to 15,000rpm and the stirring continued for a further 3 minutes.

The gel is then poured into a pint jar which is subsequently rocked andswirled for 30 seconds to remove most of the air bubbles. The jar isthen capped tight and put into a 25° C. water bath. After fifteenminutes and 24 hours, viscosity readings are taken using a Brookfieldviscometer with a number three spindle. The spindle is inserted to thenear side of the jar and then moved to the center. Then viscosityreadings are taken from low to high stirring rates: at 10 rpm after 40seconds at this speed, at 20 rpm after 30 seconds, at 50 rpm after 20seconds and at 100 rpm after 15 seconds. After the viscosity readings,the temperature in the rear side of jar is usually about 30° C. and atthe center 35° C.

After the 10 minute reading, the jar is capped and set in a 25° C. waterbath until the 24 hour reading.

The Alkyd Resin Gel Test

Alkyd resins are in general, polyesters derived from fatty acids,polyols such glycerol or glycol, and dicarboxylic acids, usuallyphthalic anhydride. The resins used in the present tests were long oilalkyd resins, which are most commonly used for general purposeindustrial coatings. They were obtained from Reichhold Chemical underthe name Beckosol P-296-70 with a computer code number 10-045. Theproduct contains 30% mineral spirits as a solvent. The solid resin (70%is derived using about 65% soybean oil, 24% phthalic anhydride and 11%glycerol. As such, the product meets federal specification,classification TTR 2660A, Type Class A, vinyl compatible. ItsGardner-Holdt viscosity is Y-Z₂. The viscosity of the products suppliedwas apparently significantly different on the Brookfield scale.

In the test procedure, 1.25 g of organic clay is slowly added to 88 gresin, while stirring it with a high speed, i.e., high shear mixer (witha drill press equipped with a circular Cowle's blade). After mixing forabout two to five minutes, a polar solvent mixture consisting of 95%propylene carbonate and 5% water is added in an amount equalling 33% ofthe clay while stirring to give optimum dispersion and highestviscosity. Thereafter, stirring is continued for an additional fiveminutes. The resulting gel is then thinned using a solvent, i.e., 10 godorless mineral spirit, to reduce the viscosity. Viscosity measurementsof the resulting mixtures are made in 18 to 24 hours after the airbubbles formed during the stirring rose out of the liquid gels.

In the alkyd resin gel tests, three batches of Beckosol P-296-70 wereused. Their viscosity characteristics, as determined by the Brookfieldviscosimeter, were somewhat different as indicated by the followingtabulation:

    ______________________________________                                                        Brookfield Viscosities,                                                       cps of Long Oil Alkyd                                                         Resins After 18-24                                            Batch Identification                                                                          Hours (at Various                                             of Resin        Stirring Rates, rpm)                                          Beckosol P-296-70                                                                             (10)    (20)    (50)  (100)                                   ______________________________________                                        A               2800    3000    3120  3200                                    B               2000    2200    2400  2400                                    C               2400    2500    2640  2620                                    ______________________________________                                    

The different batches of the resin showed different responses to thetetraalkyl phosphonium clay gellants. Therefore, strictly speaking, thedata are comparable only when the same batch of resin was used.

The response of these resins to organic clay gellants was determinedusing available commercial quaternary dimethyl dihydrogenated tallowammonium clays, as standards. The Astratone 40 standard is manufacturedby the Georgia Kaolin Co. starting with refined sodium montmorillonite,basically the same clay which was used in our Examples 3-11. The Bentone38 standard is manufactured by N. L. Industries from refined sodiumhectorite, a clay similar to the one used in Example 1. Theeffectiveness of these two ammonium clays in the three batches of alkydresin was as shown by the following tabulation:

    ______________________________________                                                             Brookfield Viscosities,                                           Di-Batch Iden-                                                                            of Long Oil Alkyd                                        Dimethyl tification  Resins After 18-24 Hrs.                                  tallow   of Resin    At Various Stirring                                      Ammonium Beckosol    Rates, (rpm)                                             Clay     P-296-70    (10)    (20)  (50)  (100)                                ______________________________________                                        Astratone-40                                                                           A           6000    5400  5120  4940                                 Bentone-38                                                                             A           6800    6200  5680  5320                                 Astratone-40                                                                           B           3200    3100  3040  2960                                 Bentone-38                                                                             B           4400    4000  3760  3540                                 Astratone-40                                                                           C           3400    3400  3280  3120                                 Bentone-38                                                                             C           4400    4200  3920  3740                                 ______________________________________                                    

EXAMPLE 18 -- Gelling Effectiveness of Higher Monoalkyl Trimethyl andTriethyl Phosphonium Montmorillonites

The swelling of styrene and the gelling of toluene and a long oil alkydresin (C) by the quaternary higher monoalkyl phosphonium clays ofExample 3, Table III was studied in routine laboratory tests. Theresults obtained are shown in Table XI.

Overall, the data show that these mono- C₁₄₋₂₀ alkyl phosphonium claysare effective gelling agents. The styrene swelling showed no definitecorrelation with the length of the higher n-alkyl group. The toluene andalkyd resin gelling seemed to be at a maximum in the C₁₄₋₁₆ alkyl range(Seq. Nos. 5 and 6). In the case of the dodecyl

                                      TABLE XI                                    __________________________________________________________________________    STYRENE SWELLING, TOLUENE AND ALKYD RESIN GELLING EFFICIENCY OF HIGHER        MONOALKYL TRIMETHYL AND TRIETHYL PHOSPHONIUM MONTMORILLONITES                 [CH.sub.3 (CH.sub.2 O).sub.0-1 P.sup.+ C.sub.m H.sub.2m+1 ] Clay.sup.- ;      m = 11-20                                                                                   Styrene                                                                             Brookfield Viscosities, cps, At Various Stirring                              Rates (rpm)                            Batch              Structure     Swell 2% Solids in Toluene    1.4% Solids in Alkyd                                                                         ofsin              Seq.                                                                             of Quaternary                                                                            Ml.   After 15 Mins.                                                                            After 24 Hrs.                                                                             After 18-24                                                                                  Alkyd              No.                                                                              Cation in Clay                                                                           2Hr                                                                              24Hr                                                                             (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                              (20)                                                                              (50)                                                                             (100)                                                                             Used               __________________________________________________________________________    1  [(CH.sub.3).sub.3 P.sup.+ C.sub.11 H.sub.23 ]                                                   42                                                                               19                                                                               10                                                                               10                                                                              Gel Unstable                                                                              2600                                                                              2600                                                                              2880                                                                             2860                                                                              A                  2  [(CH.sub.3).sub.3 P.sup.+ C.sub.14 H.sub. 29 ]                                           28 28                         4000                                                                              4400                                                                              4240                                                                             4040                                                                              A                  3  [(CH.sub.3).sub.3 P.sup.+ C.sub.20 H.sub.41                                              31 30 1320                                                                             740                                                                              304                                                                              152                                                                              1600                                                                             720                                                                              304                                                                              176                                                                              7600                                                                              7000                                                                              5680                                                                             5640                                                                              A                  4  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.12 H.sub.25 ]                                     20 20  392                                                                             188                                                                               77                                                                               50                                                                               178                                                                              90                                                                               43                                                                               31                                                                              7200                                                                              6200                                                                              5440                                                                             5040                                                                              A                  5  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.16 H.sub.33 ]                                     29 28 1968                                                                             900                                                                              387                                                                              179                                                                              1416                                                                             672                                                                              298                                                                              204                                                                              9600                                                                              8000                                                                              6640                                                                             6060                                                                              A                  6  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.18 H.sub.37 ]                                     30 29 1816                                                                             880                                                                              326                                                                              171                                                                              1344                                                                             672                                                                              288                                                                              157                                                                              10,000                                                                            8000                                                                              6960                                                                             6160                                                                              A                  7  [(C.sub.2 H.sub.5).sub.3 P.sup.+ C.sub.20 H.sub.41 ]                                     26 24 1320                                                                             612                                                                              251                                                                              126                                                                               784                                                                             428                                                                              210                                                                              116                                                                              5200                                                                              4800                                                                              4320                                                                             4140                                                                              A                  __________________________________________________________________________     triethyl phosphonium clay (Seq. No. 4), a good alkyl resin gelling but     poor toluene gelling was observed. The behavior of the docosyl trimethyl     and triethyl phosphonium derivatives (Seq. Nos. 3 and 7) was similar.     However, the viscosity of the trimethyl phosphonium gel increased with     time while that of the triethyl derivative decreased.

EXAMPLE 19 -- Gelling Effectiveness of Higner Monoalkyl TributylPhosphonium Montmorillonites

The swelling of styrene and the gelling of toluene and some long oilalkyl resins of the higher monoalkyl tributyl monoalkyl phosphoniumclays of Example 4, Table IV, was determined as shown in Table XII.

The data in general indicate that all clay derivatives prepared areeffective gelling agents. It is interesting to note that the higheralkyl tri-n-butyl phosphonium clays are less effective in gellingtoluene than the corresponding tri-i-butyl compounds (Seq. Nos. 1 and 2versus 3 and 5). The dodecyl tri-i-butyl phosphonium clay is the bestcompound for gelling toluene (Seq. No. 3).

EXAMPLE 20 -- Gelling Effectiveness of Docosyl Lower TrialkylPhosphonium Montmorillonite Clays

The docosyl tri-C₁₋₄ -alkyl phosphonium clays of Example 5, Table V wereevaluated for their gelling efficiency in routine tests. The results areshown in Table XIII.

The data show that the docosyl lower trialkyl compounds are allgellants. Their swelling in styrene increases as the lower trialkylgroups increase from trimethyl to tributyl (from Seq. No. 1 to 5). Thesame trend is observed with regard to their efficiency in gelling a longoil alkyl resin. The trimethyl compound has little effect in gelling thealkyd (Seq. No. 1).

                                      TABLE XII                                   __________________________________________________________________________    STYRENE SWELLING, TOLUENE AND ALKYD RESIN GELLING OF TRI-n-                   BUTYL AND TRI-i-BUTYL PHOSPHONIUM MONTMORILLONITES                            [(C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.m H.sub.2m+1 ] Clay.sup.- ; m =        12-18                                                                                       Styrene                                                                              Brookfield Viscosities, cps, At Various Stirring                              Rates, (rpm)                          Batch              Structure of  Swell  2% Solids in Toluene    1.4% Solids in Alkyd                                                                        ofsin              Seq.                                                                             Quaternary Cation                                                                        Ml.    After 15 Mins.                                                                            After 24 Hrs.                                                                             After 18-24                                                                                 Alkyd              No.                                                                              on Clay    2 Hr                                                                             24 Hr                                                                             (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                              (20)                                                                              (50)                                                                             (100)                                                                            Used               __________________________________________________________________________    1  [(n-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.12 H.sub.25 ]                                   30 30   440                                                                             196                                                                               80                                                                              43 240                                                                              120                                                                               46                                                                              49 7600                                                                              6800                                                                              6000                                                                             5440                                                                             A                  2  [(n-C.sub.4 H.sub.9).sub. 3 P.sup.+ C.sub.16 H.sub.33 ]                                  32 32   416                                                                             184                                                                               77                                                                              42 184                                                                               76                                                                               38                                                                              17 14000                                                                             11000                                                                             8400                                                                             7200                                                                             A                  3  [(i-C.sub.3 H.sub.9).sub.3 P.sup.+ C.sub.12 H.sub.25 ]                                          1120                                                                             580                                                                              172                                                                              84 840                                                                              430                                                                              172                                                                              94 5200                                                                              4800                                                                              4560                                                                             4300                                                                             C                  4  [(i-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.14 H.sub.29 ]                                           680                                                                             260                                                                              104                                                                              60 440                                                                              220                                                                              104                                                                              64 5800                                                                              5500                                                                              4960                                                                             4560                                                                             C                  5  [(i-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.16 H.sub.33 ]                                           760                                                                             360                                                                              136                                                                              74 660                                                                              320                                                                              152                                                                              88 5000                                                                              4700                                                                              4480                                                                             4200                                                                             C                  6  [(i-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.18 H.sub.37 ]                                   35 34  1200                                                                             480                                                                              176                                                                              96 496                                                                              248                                                                              128                                                                              68 5200                                                                              4700                                                                              4200                                                                             3800                                                                             B                  __________________________________________________________________________

                                      TABLE XIII                                  __________________________________________________________________________    STYRENE SWELLING, TOLUENE AND ALKYD RESIN GELLING EFFICIENCY OF               DOCOSYL LOWER TRIALKYL PHOSPHONIUM MONTMORILLONITES                           [(C.sub.n H.sub.2n+ 1).sub.3 P.sup.+ C.sub.22 H.sub.45 ] Clay.sup.- ;         n-1-4                                                                                       Styrene                                                                              Brookfield Viscosities, cps, At Various Stirring                              Rates, (rpm)                          Batch              Structure of  Swell  2% Solids in Toluene    1.4% Solids in Alkyd                                                                        ofsin              Seq.                                                                             Quaternary Cation                                                                        Ml.    After 15 Mins. After 24 Hrs.                                                                          After 18-24                                                                                 Alkyd              No.                                                                              on Clay    2Hr                                                                              24Hr                                                                              (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                             (10)                                                                             (20)                                                                              (50)                                                                             (100)                                                                            Used               __________________________________________________________________________    1  [(CH.sub.3).sub.3 P.sup.+ C.sub.22 H.sub.45 ]                                            30 30  232                                                                               92                                                                               42                                                                              29  352                                                                             164                                                                              83 62  4400                                                                              4300                                                                             4300                                                                             4500                                                                             A                  2  [(C.sub.2 H.sub.5).sub.3 P.sup. + C.sub.22 H.sub.45 ]                                    32 32  720                                                                              560                                                                              208                                                                              104                                                                              1000                                                                             560                                                                              208                                                                              104                                                                               7600                                                                             7000                                                                              5840                                                                             5680                                                                             A                  3  [(n-C.sub.3 H.sub.7).sub.3 P.sup.+ C.sub.22 H.sub.45 ]                                   41 40  760                                                                              340                                                                              133                                                                              70  272                                                                             144                                                                              70 45  7600                                                                             7000                                                                              6400                                                                             6040                                                                             A                  4  [(i-C.sub.3 H.sub.7).sub.3 P.sup.+ C.sub.22 H.sub.45 ]                                   44 42  600                                                                              268                                                                              114                                                                              66  592                                                                             292                                                                              134                                                                              76                                  4  [(n-C.sub.4 H.sub.9).sub.3 P.sup.+ C.sub.22 H.sub.45 ]                                   47 47  224                                                                              100                                                                              54 34  256                                                                             124                                                                              64 35 14000                                                                             11000                                                                             8720                                                                             7360                                                                             A                  __________________________________________________________________________

EXAMPLE 21 -- Gelling Effectiveness of Higher Dialkyl Dimethyl andDiethyl Phosphonium Montmorillonite Clays

The di-C₈₋₁₈ -alkyl phosphonium clays of Example 6, Table VI wereevaluated for swelling and gelling in the usual routine tests. The dataobtained are shown in Table XIV.

The results indicate that the higher dialkyl phosphonium clays of TableXIV are surprisingly less effective in gelling toluene than themonoalkyl derivatives of Table XII. The alkyd resin gellingeffectiveness of the higher dialkyl compounds is comparable to that ofthe higher monoalkyl compounds.

                                      TABLE XIV                                   __________________________________________________________________________    STYRENE SWELLING, TOLUENE AND ALKYD RESIN GELLING EFFICIENCY                  OF HIGHER DIALKYL DIMETHYL AND DIETHYL PHOSPHONIUM MONTMORILLONITES           (C.sub.r H.sub.2r+1).sub.2 P.sup.+ (CH.sub.2).sub.0-1 CH.sub.3 ; r =          8-18                                                                                        Styrene                                                                             Brookfield Viscosities, cps, At Various Stirring                              Rates (rpm)                           Batch               Structure of  Swell, ml                                                                           2% Solids in Toluene    1.4% Solids in Alkyd                                                                        ofsin               Seg.                                                                             Quaternary Cation                                                                        (After Hrs)                                                                         After 15 Mins.                                                                            After 24 Hrs.                                                                             After 18-24                                                                                 Alkyd               No.                                                                               on Clay   (2)                                                                              (24)                                                                             (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                             (20)                                                                             (50)                                                                             (100)                                                                            (10)                                                                              (20)                                                                              (50)                                                                             (100)                                                                            Used                __________________________________________________________________________    1  [(CH.sub.3).sub.2 P.sup.+ (C.sub.8 H.sub.17).sub.2 ]                                     23 23 232                                                                              100                                                                              45 25    Gel Unstable                                                                            7600                                                                             6800                                                                              5680                                                                             5600                                                                             A                   2  [(CH.sub.3).sub.2 P.sup.+ (C.sub.10 H.sub.21 ).sub.2 ]                                   19 19 328                                                                              152                                                                              64 37 160                                                                              96 27 14 12000                                                                             9600                                                                              7760                                                                             6840                                                                             A                   3  [(CH.sub.3).sub.2 P.sup.+ (C.sub.12 H.sub.25).sub.2 ]                                    23 23 120                                                                               56                                                                              26 24    Gel Unstable                                                                           11600                                                                             10000                                                                             8320                                                                             7300                                                                             A                   4  [(C.sub.2 H.sub.5).sub.2 P.sup.+ (C.sub.18 H.sub.37).sub.2 ]                             30 30 240                                                                              208                                                                              91 52    Gel Unstable                                                                            9600                                                                             8000                                                                              6880                                                                             6440                                                                             A                   __________________________________________________________________________

EXAMPLE 22 -- Gelling Efficiency in Alkyd Resin of Quaternary HigherTrialkyl Phosphonium Montmorillonite Clays

The quaternary tri-C₆₋₁₀ -alkyl phosphonium clays of Example 7, TableVII were examined for their gelling efficiencies in the previouslydescribed routine tests. All the clays of this group were foundineffective gellants for toluene. The observed toluene viscosities werebelow 200 cps. However, some of the products were effective in gelling along oil alkyd resin as shown by Table XV.

The results clearly demonstrate the superior gellant effectiveness ofthe methyl and ethyl trioctyl phosphonium clays in an alkyd resin amongthe quaternary higher trialkyl phosphonium clays tested. (Seq. Nos. 2and 3). The gellant effectiveness of the trioctyl group is rapidlydecreased as the chain length of the fourth alkyl group is increasedbeyond two carbons (Seq. Nos. 3 versus 4 and 5). As the chain length ofthe fourth alkyl group is increased beyond four carbons, quaternarytrioctyl phosphonium clays possess no gellant capacity in the alkydresin. (Seq. Nos. 6 and 7). Similarly, the benzyltrioctyl clay productis not an alkyd gellant either (Seq. No. 8).

Another surprising finding is the rapid decrease in gelling capacitywhen the trialkyl group is decreased to six carbons or increased to tencarbons per chain. Both the methyl trihexyl and methyl tridecylphosphonium clays are significantly less effective alkyd gellants thanthe corresponding methyl trioctyl quaternary clay derivates (Seq. Nos. 4and 7 versus 2).

                  TABLE XV                                                        ______________________________________                                        GEL STRENGTH IN AN ALKYD RESIN OF                                             QUATERNARY HIGHER TRI-C.sub.6-10 -ALKYL                                       PHOSPHONIUM MONTMORILLONITE CLAYS                                             [(C.sub.j H.sub.2j+1).sub.3 P.sup.+ C.sub.k H.sub.2k+1 ] Clay.sup.- ; j =     6-10; k = 1-6                                                                                          Brookfield Viscosities.                                                       cps. After 18-24 Hrs. of                                                      Alkyd Resin Containing                                                        1.4% Clay Solids (at                                                          Various Stirring                                     Seq. Structure of        Rates rpm)                                           No.  Quarternary Cation  (10)   (20) (50) (100)                               ______________________________________                                        1    [(C.sub.6 H.sub.13).sub.3 P.sup.+ CH.sub.3 ]                                                      3200   3400 3360 3400                                2    [(C.sub.8 H.sub.17).sub.3 P.sup.+ CH.sub.3 ]                                                      5600   5200 4960 4560                                3    [(C.sub.8 H.sub.17).sub.3 P.sup.+ C.sub.2 H.sub.5 ]                                               6000   5400 4920 4560                                4    [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.3 H.sub.7 ]                                             4000   3600 3440 3080                                5    [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.9 H.sub.9 ]                                             3600   3500 3280 3120                                6    [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.5 H.sub.11 ]                                            2400   2600 2760 2620                                7    [(C.sub.8 H.sub.17).sub.3 P.sup.+ n-C.sub.6 H.sub.13 ]                                            2400   2500 2640 2620                                      ##STR7##           2600   2700 2880 2920                                9    [(C.sub.10 H.sub.21).sub.3 P.sup.+ CH.sub.3 ]                                                     3600   3200 3120 2840                                ______________________________________                                    

the adverse effect of increasing the carbon number of the fourth alkylsubstituent of quaternary trioctyl phosphonium clays is especiallyinteresting since this structural change of the phosphonium groups doesnot affect the interplanar distance of their clay derivatives. It isproposed that in the case of these and similar higher trialkylphosphonium clays the decreased gelling efficiency is due to increasedsteric crowding, which inhibits the polar interactions involved in thegelling process. The way steric factors may play a role is indicated bythe proposed position of the hexyl trioctyl phosphonium group in theinterplanar space. As shown in Example 7, FIG. 1, the hexyl group isoriented parallel to the surface and as such its dimensions willinfluence the degree of the polar interactions of polar additives orpolar fluids to be gelled with the phosphonium and silicate groups. Oncesuch polar interactions are completely blocked, no gelling will occur.

What is claimed is:
 1. Tetraalkyl phosphonium clays of the formula:

    [R.sub.4 P.sup.+ ]Clay.sup.-

wherein the four R groups are C₁ -C₁₀₀ aliphatic hydrocarbyl radicalsselected in such a manner that at least one of the R groups issubstituted.
 2. The composition of claim 1 wherein the Clay⁻¹ is anegatively charged aluminosilicate of the layer and chain typestructure.
 3. The composition of claim 2 wherein the aliphatichydrocarbyl radicals are alkyl radicals at least one of which issubstituted and, at least one of which contains at least 8 carbon atoms.4. The composition of claim 3 wherein the substituent is on an alkylradical other than the alkyl radical containing at least 8 carbon atoms.5. The composition of claim 1 wherein the substituent on the R groups isselected from the group consisting of phosphino, amino, cyano andhydroxy substituents and combinations thereof.
 6. Tetraalkyl phosphoniumclays of the formula:

    {R.sub.x P.sup.+ [QZ].sub.y }Clay.sup.-

wherein R is a C₁ -C₁₀₀ monovalent aliphatic hydrocarbyl radical, Q is aC₁ -C₁₀₀ divalent aliphatic hydrocarbyl radical, Z is a heteroatomicradical containing up to 40 carbon atoms and x and y are 1 to 3providing that x + y equal
 4. 7. The composition of claim 6 wherein Q isa C₁ -C₄₀ divalent aliphatic hydrocarbyl radical and Z is a heteroatomicradical containing up to 40 carbon atoms selected from the groupconsisting of phosphino, amino, cyano and hydroxy groups.
 8. Thecomposition of claim 6 wherein Clay⁻ is a negatively charged layeredaluminosilicate.
 9. The composition of claim 8 wherein the negativelycharged layered aluminosilicate is a negatively charged montmorillonite.10. The composition of claim 6 wherein at least one R is a C₈ -C₁₀₀aliphatic hydrocarbyl radical and Clay⁻ is a negatively chargedaluminosilicate.
 11. The composition of claim 10 wherein at least one Rgroup is allyl.
 12. The composition of claim 10 wherein the C₁ -C₁₀₀aliphatic hydrocarbyl radical R groups are selected from the groupconsisting of alkyl and alkenyl.
 13. The composition of claim 6 whereinQ is selected from the group consisting of alkylene and alkenylene. 14.Diphenylphosphino substituted tetraalkyl phosphonium clays of theformula: ##STR8## wherein R is a C₁ -C₁₀₀ monovalent aliphatichydrocarbyl radical, x and y are 1 to 3, providing that x + y equal 4and z is 1 to
 40. 15. The compositions of claim 14 wherein Z is 6 to 14.16. 14-Diphenylphosphinotetradecyl triethyl phosphonium montmorillonite.17. Dialkylamino substituted tetraalkyl phosphonium clays of theformula:

    {R.sub.x P.sup.+ [(CH.sub.2).sub.z N(C.sub.q H.sub.2q+1).sub.2 ].sub.y }Clay.sup.-

wherein R is a C₁ -C₁₀₀ monovalent aliphatic hydrocarbyl radical; q is 0to 18; x and y are 1 to 3, providing that x plus y equal 4; z is 1 to40.
 18. The compositions of claim 17 wherein q is 1 to
 18. 19. Thecompositions of claim 17 wherein z is
 3. 20. Bis-dimethylaminopropyldodecyl isobutyl phosphonium montmorillonite.
 21. Cyano substitutedtetraalkyl phosphonium clays of the formula:

    {R.sub.x P.sup.+ [(CH.sub.2).sub.z CN].sub.y }Clay.sup.-

wherein R is a C₁ -C₁₀₀ monovalent aliphatic hydrocarbyl radical; x andy are 1 to 3, providing that x plus y are 4; z is 1 to
 40. 22. Thecompositions of claim 21 wherein z is
 2. 23. Tris-cyanoethyl dodecylphosphonium montmorillonite.
 24. Hydroxy substituted tetraalkylphosphonium clays of the formula:

    {R.sub.x P.sup.+ [(CH.sub.2).sub.z OH].sub.y ]Clay.sup.-

wherein R is a C₁ -C₁₀₀ monovalent aliphatic hydrocarbyl radical; x andy are 1 to 3, providing that x plus y are 4; z is 1 to
 40. 25. Thecompositions of claim 24 wherein z is 1 to
 3. 26. Bis-hydroxypropyloctadecyl isobutyl phosphonium montmorillonite.
 27. Bis-hydroxypropyldocosyl isobutyl phosphonium montmorillonite.